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§ 217 StGB reiht sich in andere kriminalpolitische Projekte des Gesetzgebers ein, die sich dem Einwand des fehlenden Rechtsgutsbezugs ausgesetzt sehen.
Die Untersuchung zeigt auf, dass der Gesetzgeber mit der Einführung des § 217 StGB den Zweck des Strafrechts als „ultima-ratio“ des Rechtsgüterschutzes verfehlt hat. Auch wenn er mit der Norm den Schutz von Leben und Autonomie bezweckt hat, ist ihm die Umsetzung des Schutzes dieser Rechtsgüter nicht gelungen. Die Vorschrift dient vielmehr dem Zweck der Verhinderung einer Suizidkultur. Nach der systemkritischen Rechtsgutslehre kann ein solcher „moralischer“ Zweck jedoch kein strafrechtlich zu schützendes Rechtsgut darstellen.
Da eine Aufhebung der Vorschrift durch das Bundesverfassungsgericht wenig wahrscheinlich erscheint, schließt sich der Rechtsgutsdiskussion eine praxisorientierte Auslegung der Norm unter dem Gesichtspunkt des überindividuellen Zwecks, der Verhinderung einer Suizidkultur, an.
Sprachliche Kompetenzen spielen für den Bildungserfolg von Schülerinnen und Schülern eine grundlegende Rolle. Die besonderen sprachlichen Anforderungen der Bildungsinstitutionen stellen einige Kinder und Jugendliche vor Herausforderungen, die ihnen eine erfolgreiche Bildungslaufbahn erschweren. Um allen Lernenden den Zugang zu Bildung zu gewähren, sollten sprachliche Kompetenzen im Rahmen des schulischen Alltags und insbesondere des Fachunterrichts gefördert werden. Um Lehrerinnen und Lehrer für diese Aufgabe zu qualifizieren, sind wirksame Fortbildungen essenziell. Fortbildungen sind allerdings nicht per se wirksam. Vielmehr wird ihre Wirksamkeit von einer Vielzahl von Faktoren bedingt und sie variiert je nach Bereich. Inwieweit Merkmale und Bedingungen wirksamer Fortbildungen sowie Gesamteffekte, die bereichsübergreifend und für einige spezifische Bereiche bekannt sind, auch für Lehrkräftefortbildungen zur fachintegrierten Sprachförderung gelten, ist bisher ungeklärt. Im deutschen Raum fehlt es an Evaluationsstudien, die die Wirksamkeit solcher Fortbildungen und ihre Gelingensbedingungen untersuchen. Im internationalen Raum sind solche Studien zwar vorhanden, in ihrer Gesamtheit jedoch schwer zu überblicken, sodass sich bislang keine umfassenden Aussagen über den Erfolg dieser Fortbildungen treffen lassen. Vor diesem Hintergrund beschäftigt sich die vorliegende Dissertation anhand von drei Teilstudien mit der Wirksamkeit von Fortbildungen, die Lehrkräfte dafür qualifizieren sollen, eine in die Fächer und Lernbereiche der Schule integrierte Sprachförderung umzusetzen.
In einem systematischen Review (Studie 1) wurden die vorhandenen englischsprachigen Studien, in denen solche Fortbildungsmaßnahmen evaluiert wurden, systematisch ausgewertet. Insgesamt wurden 38 Studien einbezogen. Anhand dieser wurde qualitativ-inhaltsanalytisch untersucht, ob Merkmale wirksamer Lehrkräftefortbildung, die aus der fächerübergreifenden Forschung bekannt sind, für das spezifische Feld der Sprachförderung im Fachunterricht ebenfalls von Bedeutung sind oder ob dort andere Merkmale eine Rolle spielen. Die Studien deuten darauf hin, dass alle evaluierten Fortbildungen zumindest in gewissem Maß wirksam waren. Im Ergebnis zeigte sich, dass die Maßnahmen viele Eigenschaften teilen, die für eine erfolgreiche Lehrkräftefortbildung über verschiedene Fächer hinweg wichtig sind. Sie enthalten darüber hinaus einige Merkmale, die spezifisch für Fortbildung zur fachintegrierten Sprachförderung zu sein scheinen. Das Review stützt die Annahme, dass Fortbildungen die Kognitionen und die Unterrichtspraxis von Lehrkräften verändern und den Schülerinnen und Schülern zugutekommen kann, wenn bestimmte Merkmale bei der Gestaltung und Umsetzung berücksichtigt werden.
Aufbauend auf das Review wurden mit einer Meta-Analyse (Studie 2) die Effekte aus denjenigen zehn Studien aggregiert, die sich auf quantitative Weise analysieren ließen. Es wurde der Gesamteffekt der Fortbildungen sowohl auf die Kognitionen (z. B. Überzeugungen) der Lehrkräfte als auch auf das unterrichtspraktische Handeln (z. B. Verwendung sprachförderlicher Strategien) der Lehrkräfte ermittelt. Außerdem wurde untersucht, welche Rolle Merkmale der einbezogenen Studien sowie der Fortbildungen für die Ausprägung der Effekte spielen. Die Analysen ergaben einen kleinen Fortbildungseffekt auf die Kognitionen und einen mittleren bis großen Effekt auf das unterrichtspraktische Handeln der Lehrkräfte. Studienmerkmale, die die methodische Qualität der Studien betrafen, moderierten die Effekte. Dennoch deuten die Ergebnisse darauf hin, dass Fortbildung zur fachintegrierten Sprachförderung sich günstig auf die Kognitionen und Handlungen von Lehrkräften auswirkt.
Mit einer quasi-experimentellen Tagebuchstudie (Studie 3) wurde eine in Deutschland umgesetzte Fortbildung zur integrierten Sprachförderung formativ evaluiert. Die zentrale Frage war, inwiefern die fortgebildeten Grundschullehrkräfte in der Maßnahme vermittelte Sprachförderstrategien nach eigenen Angaben häufiger anwenden als ihre Kolleginnen und Kollegen, die nicht an der Fortbildung teilgenommen hatten. Untersucht wurde außerdem, inwiefern Faktoren wie die berichtete Kooperation im Kollegium mit der berichteten Häufigkeit der Strategieanwendung zusammenhängen. Mit einem standardisierten Tagebuch wurden 59 Grundschullehrkräfte befragt. Die mehrebenenanalytische Auswertung der Daten ergab keine signifikanten Unterschiede in der angegebenen Häufigkeit der Strategieanwendung zwischen den beiden Gruppen. Allerdings wurde die Nutzung einiger Strategien häufiger berichtet, wenn die Kooperation im Kollegium höher eingeschätzt wurde. Zudem fühlten sich die fortgebildeten Lehrkräfte im Vergleich zu den nicht fortgebildeten in der Anwendung der Strategien sicherer.
Die zentralen Ergebnisse dieser Dissertation werden abschließend zusammengefasst und diskutiert. Implikationen für zukünftige Forschung, Fortbildungspraxis und Bildungspolitik werden formuliert.
Wie Computer heimisch wurden
(2019)
Mit der Einführung des Personal Computers Ende der 1970er-Jahre wurde ein neuer Markt für Konsument_innen von Computertechnologie geschaffen. Im Gegensatz zu den vorherrschenden Erzählungen über geniale Erfinder, tüchtige Unternehmer und Visionäre der Computerkultur im Silicon Valley nimmt Sophie Ehrmanntraut auch jenen Teil der amerikanischen Gesellschaft in den Blick, der Computer bis dahin nur aus den Nachrichten oder Science-Fiction-Romanen kannte. Ihre Studie zeigt: Die ersten Reaktionen der potenziellen Kundschaft waren ernüchternd – der Umgang mit Computern musste gelernt werden. Doch nicht zuletzt gezieltes Marketing verwandelte schließlich die Rechenmaschine vom selektiven Arbeitsinstrument zum Massenmedium der Informationsgesellschaft.
Was bleibt?
(2019)
In der jüdischen Familie im 19. Jahrhundert hatte das Testament primär die Funktion eines Rechtsakts. Mittels der Theorie der Gabe des französischen Anthropologen Marcel Mauss untersucht Doreen Kobelt in diesem Band, wie das Testament auch als eine Art Spiegel innerfamiliärer Veränderungen gelesen werden kann. Zentrale Bedeutung kommt dabei der Mitgift der Frau zu. Diese war im 19. Jahrhundert in der Mehrheitsgesellschaft wie auch in der innerjüdischen Debatte zunehmend umstritten.
Für die vorliegende Studie wurden 656 Testamente aus Hamburg und Altona mithilfe quantitativer und qualitativer Methoden analysiert. Neben vielen bisher unbekannten Testierenden werden auch die Familien Heine und Warburg betrachtet.
Untersuchungen zur Entwicklung und Synthese neuartiger Gelenkstäbe basierend auf Oligospiroketalen
(2019)
En se penchant sur les réécritures de l'histoire pour le citoyen dans l’espace germanique et la France des Lumières et de la Révolution, ce livre apporte un regard nouveau et distancié sur les usages publics de l’histoire aujourd'hui, en France en particulier où le débat autour du roman national reste vif. La première partie de l’ouvrage, consacrée à l’exemplarité d’une histoire illustrée de gravures qui ont durablement marqué les représentations du passé, revisite la question des grands hommes, reproduit, traduit et analyse la circulation d’exemples édifiants entre les deux espaces.
La deuxième partie traite d’un mode de représentation pédagogique de l’histoire qui suscitait, et suscite toujours, la fascination tout en posant un défi de méthode: l’usage pédagogique d’un tableau permettant de saisir d’un seul coup d’oeil toute l’histoire d’un peuple voire de l’humanité tout entière, et d’en tirer des leçons politiques. L’idée, encore structurante aujourd’hui, d’un modèle politique ou pédagogique allemand ou français d’une écriture de l’histoire couplée, ou non, à la géographie est examinée ici au prisme des contextes précis où elle a été pensée.
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.
Totalsynthese benzoannellierter Sauerstoffheterocyclen durch Mikrowellen induzierte Tandem-Sequenzen
(2019)
This thesis puts the citizen-state interaction at its center. Building on a comprehensive model incorporating various perspectives on this interaction, I derive selected research gaps. The three articles, comprising this thesis, tackle these gaps. A focal role plays the citizens’ administrative literacy, the relevant competences and knowledge necessary to successfully interact with public organizations. The first article elaborates on the different dimensions of administrative literacy and develops a survey instrument to assess these. The second study shows that public employees change their behavior according to the competences that citizens display during public encounters. They treat citizens preferentially that are well prepared and able to persuade them of their application’s potential. Thereby, they signal a higher success potential for bureaucratic success criteria which leads to the employees’ cream-skimming behavior. The third article examines the dynamics of employees’ communication strategies when recovering from a service failure. The study finds that different explanation strategies yield different effects on the client’s frustration. While accepting the responsibility and explaining the reasons for a failure alleviates the frustration and anger, refusing the responsibility leads to no or even reinforcing effects on the client’s frustration. The results emphasize the different dynamics that characterize the nature of citizen-state interactions and how they establish their short- and long-term outcomes.
A new model that links visionary leadership with team performance is
postulated. It is proposed that leader prototypicality will negatively
moderate the effect of visionary leadership on team goal monitoring and performance. This model underlines that teams will compensate for the less prototypicality of a visionary leader by engaging in more goal monitoring, which is a process that is conducive to team performance. A field study included 60 teams, 180 individuals, and 60 team leaders was conducted in Egypt. Parameters were collected on the individual level.
Aggregation measures (rwg, ICC1 & ICC2) were acceptable and the averages were calculated for each team. The proposed three-factor model exhibited a reasonable fit to the data, χ2(130) = 259.93, p-value0.01; CFI = 0.90; and RMSEA = 0.13). The hypothesized negative moderation effect of leader prototypicality on the relationship between visionary leadership and team goal monitoring was statistically significant (-0.16; s.e.= 0.06; t = -3.13; p <0.01; 95% CI: -0.31, -0.07). Results showed a significant index of moderated mediation (-0.07; s.e.= 0.05; 95% CI: -0.20, -0.01). As predicted, the indirect effect of visionary leadership on team performance mediated by team goal monitoring was more strongly positive when leader prototypicality was low (b = 0.27; s.e.= 0.16; 95% CI: 0.04, 0.68), rather than high (b = 0.13; s.e.= 0.10; 95% CI: 0.01, 0.45). A proposal for extending the dimensions of identity-based leadership is discussed. This dissertation makes four significant contributions to theory and research on leadership. First, the main contribution of this research lies in showing that visionary leadership is more strongly positively related to team performance when leader prototypicality is low, rather than high. Second, this dissertation provides a contribution toward overcoming the fragmentation in the leadership literature by desegregating the literature on visionary leadership and leader-team prototypicality. Third, team goal monitoring as a mechanism that explains the interactive effects of visionary leadership and leader prototypicality on team performance was identified. Fourth, this study tests the postulated research model in Egypt, a culture that has in the past received scant attention.
The Atlantic Meridional Overturning Circulation (AMOC) is likely the most well-known system of ocean currents on Earth, redistributing heat, nutrients and carbon over a large part of the Earth’s surface and affecting global climate as a result. Due to enhanced freshwater fluxes into the subpolar North Atlantic as a response to global warming, the AMOC is expected, and may have already started, to weaken and these changes will likely have global impacts. It is therefore of considerable relevance to improve our understanding of past and future AMOC changes. My thesis tries to answer some of the open questions in this field by giving strong evidence that the AMOC has already weakened over the last century, by narrowing future projections of this slowdown and
by studying the impacts on global surface warming.
While there have been various studies trying to reconstruct the strength of the overturning circulation in the past, often based on model simulations in combination with observations (Jackson et al., 2016, Kanzow et al., 2010) or proxies (Frajka-Williams, 2015, Latif et al., 2006), the results so far, due to lack of direct measurements, have been inconclusive. In the first paper I build on previous work that links the anomalously low sea surface temperatures (SSTs) in the North Atlantic with the reduced meridional heat transport due to a weaker AMOC. Using the output of a high-resolution global climate model, I derive a characteristic spatial and seasonal SST fingerprint of an AMOC slowdown and an improved SST-based AMOC index. The same fingerprint is seen in
the observational SSTs since the late 19th Century, giving strong evidence that since then the AMOC has slowed down. In addition, the reconstruction of the historical overturning strength with the new AMOC index agrees well with and extends the results of earlier studies as well as the direct measurements from the RAPID project and shows a strong decline of the AMOC by about 15% (3±1 Sv) since the mid-20th Century (Caesar et al., 2018).
The reconstruction of the historical overturning strength with the AMOC index enables us to weight future AMOC projections based on their skill in modeling the historical AMOC as described in the second paper of this thesis (Olson et al., 2018). Using Bayesian model averaging we considerably narrow the projections of the CMIP5 ensemble to a decrease of -4.0 Sv and -6.8 Sv between the years 1960-1999 and 2060-2099 for the RCP4.5 and RCP8.5 emission scenarios, respectively. These values fit to, yet are at the lower end of, previously published estimates.
In the third paper I examine how the AMOC slowdown affects the global mean surface temperature (GMST) with a focus on how it will change the ocean heat uptake (OHC). Accounting for the effect of changes in the radiative forcing on the GMST, I test how AMOC variations correlate with the residual part of surface temperature changes in the past. I find that the correlation is positive which fits the understanding that the deep-water formation that is important in driving the AMOC cools the deep ocean and therefore warms the surface (Caesar et al., 2019). The future weakening of the overturning circulation could therefore delay global surface warming.
Due to nonlinear behavior and scale specific changes it can be difficult to study the dominant processes and modes that drive climate variability. In the fourth paper we develop and test a new technique based on the wavelet multiscale correlation (WMC) similarity measure to study climate variability on different temporal and spatial scales (Agarwal et al., 2018). In a fifth contribution to my thesis this method is applied to the observed sea surface temperatures. The results reconfirm well-known relations between SST anomalies such as the El Niño-Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO) on inter-annual and decadal timescales, respectively. They
furthermore give new insights into the characteristics and origins of long-range teleconnections, for example, that the teleconnection between ENSO and Indian Ocean dipole exist mainly between the northern part of the ENSO tongue and the equatorial Indian Ocean, and provides therefore valuable knowledge about the regions that are necessary to include when modeling regional climate variability at a certain scale (Agarwal et al., 2019).
In summary, my PhD thesis investigates past and future AMOC variability and its effects on global mean surface temperature by utilizing a combination of observational sea surface data and the output of historical and future climate model simulations from both the high-resolution CM2.6 model as well as the CMIP5 ensemble. It further includes the development and validation of a new method to study climate variability, that, applied to the observed sea surface temperatures, gives new insight about teleconnections in the Earth System. My findings provide evidence that the AMOC has already slowed down, will continue to do so in the future, and will impact the global mean temperature. Further impacts of an AMOC slowdown may include increased sea-level rise at the U.S. east coast (Ezer, 2015), heat extremes in Europe (Duchez et al., 2016) and increased storm activity in the North Atlantic region (Jackson et al., 2015), all of which have significant socio-economic implications.
This thesis covers the synthesis of conjugates of 2-Deoxy-D-ribose-5-phosphate aldolase (DERA) with suitable polymers and the subsequent immobilization of these conjugates in thin films via two different approaches.
2-Deoxy-D-ribose-5-phosphate aldolase (DERA) is a biocatalyst that is capable of converting acetaldehyde and a second aldehyde as acceptor into enantiomerically pure mono- and diyhydroxyaldehydes, which are important structural motifs in a number of pharmaceutically active compounds. Conjugation and immobilization renders the enzyme applicable for utilization in a continuously run biocatalytic process which avoids the common problem of product inhibition. Within this thesis, conjugates of DERA and poly(N-isopropylacrylamide) (PNIPAm) for immobilization via a self-assembly approach were synthesized and isolated, as well as conjugates with poly(N,N-dimethylacrylamide) (PDMAA) for a simplified and scalable spray-coating approach. For the DERA/PNIPAm-conjugates different synthesis routes were tested, including grafting-from and grafting-to, both being common methods for the conjugation. Furthermore, both lysines and cysteines were addressed for the conjugation in order to find optimum conjugation conditions. It turned out that conjugation via lysine causes severe activity loss as one lysine plays a key role in the catalyzing mechanism. The conjugation via the cysteines by a grafting-to approach using pyridyl disulfide (PDS) end-group functionalized polymers led to high conjugation efficiencies in the presence of polymer solubilizing NaSCN. The resulting conjugates maintained enzymatic activity and also gained high acetaldehyde tolerance which is necessary for their use later on in an industrial relevant process after their immobilization.
The resulting DERA/PNIPAm conjugates exhibited enhanced interfacial activity at the air/water interface compared to the single components, which is an important pre-requisite for the immobilization via the self-assembly approach. Conjugates with longer polymer chains formed homogeneous films on silicon wafers and glass slides while the ones with short chains could only form isolated aggregates. On top of that, long chain conjugates showed better activity maintenance upon the immobilization.
The crosslinking of conjugates, as well as their fixation on the support materials, are important for the mechanical stability of the films obtained from the self-assembly process. Therefore, in a second step, we introduced the UV-crosslinkable monomer DMMIBA to the PNIPAm polymers to be used for conjugation. The introduction of DMMIBA reduced the lower critical solution temperature (LCST) of the polymer and thus the water solubility at ambient conditions, resulting in lower conjugation efficiencies and in turn slightly poorer acetaldehyde tolerance of the resulting conjugates. Unlike the DERA/PNIPAm, the conjugates from the copolymer P(NIPAM-co-DMMIBA) formed continuous, homogenous films only after the crosslinking step via UV-treatment. For a firm binding of the crosslinked films, a functionalization protocol for the model support material cyclic olefin copolymer (COC) and the final target support, PAN based membranes, was developed that introduces analogue UV-reactive groups to the support surface. The conjugates immobilized on the modified COC films maintained enzymatic activity and showed good mechanical stability after several cycles of activity assessment. Conjugates with longer polymer chains, however, showed a higher degree of crosslinking after the UV-treatment leading to a pronounced loss of activity. A porous PAN membrane onto which the conjugates were immobilized as well, was finally transferred to a dead end filtration membrane module to catalyze the aldol reaction of the industrially relevant mixture of acetaldehyde and hexanal in a continuous mode. Mono aldol product was detectable, but yields were comparably low and the operational stability needs to be further improved
Another approach towards immobilization of DERA conjugates that was followed, was to generate the conjugates in situ by simply mixing enzyme and polymer and spray coat the mixture onto the membrane support. Compared to the previous approach, the focus was more put on simplicity and a possible scalability of the immobilization. Conjugates were thus only generated in-situ and not further isolated and characterized. For the conjugation, PDMAA equipped with N-2-thiolactone acrylamide (TlaAm) side chains was used, an amine-reactive comonomer that can react with the lysine residues of DERA, as well as with amino groups introduced to a desired support surface. Furthermore disulfide formation after hydrolysis of the Tla groups causes a crosslinking effect. The synthesized copolymer poly(N,N-Dimethylacrylamide-co-N-2-thiolactone acrylamide) (P(DMAA-co-TlaAm)) thus serves a multiple purpose including protein binding, crosslinking and binding to support materials. The mixture of DERA and polymer could be immobilized on the PAN support by spray-coating under partial maintenance of enzymatic activity. To improve the acetaldehyde tolerance, the polymer in used was further equipped with cysteine reactive PDS end-groups that had been used for the conjugation as described in the first part of the thesis. The generated conjugates indeed showed good acetaldehyde tolerance and were thus used to be coated onto PAN membrane supports. Post treatment with a basic aqueous solution of H2O2 was supposed to further crosslink the spray-coated film hydrolysis and oxidation of the thiolactone groups. However, a washing off of the material was observed. Optimization is thus still necessary.
During lower sea levels in glacial periods, deep permafrost formed on large continental shelf areas of the Arctic Ocean. Subsequent sea level rise and coastal erosion created subsea permafrost, which generally degrades after inundation under the influence of a complex suite of marine, near-shore processes. Global warming is especially pronounced in the Arctic, and will increase the transition to and the degradation of subsea permafrost, with implications for atmospheric climate forcing, offshore infrastructure, and aquatic ecosystems.
This thesis combines new geophysical, borehole observational and modelling approaches to enhance our understanding of subsea permafrost dynamics. Three specific areas for advancement were identified: (I) sparsity of observational data, (II) lacking implementation of salt infiltration mechanisms in models, and (III) poor understanding of the regional differences in key driving parameters. This study tested the combination of spectral ratios of the ambient vibration seismic wavefield, together with estimated shear wave velocity from seismic interferometry analysis, for estimating the thickness of the unfrozen sediment overlying the ice-bonded permafrost offshore. Mesoscale numerical calculations (10^1 to 10^2 m, thousands of years) were employed to develop and solve the coupled heat diffusion and salt transport equations including phase change effects. Model soil parameters were constrained by borehole data, and the impact of a variety of influences during the transgression was tested in modelling studies. In addition, two inversion schemes (particle swarm optimization and a least-square method) were used to reconstruct temperature histories for the past 200-300 years in the Laptev Sea region in Siberia from two permafrost borehole temperature records. These data were evaluated against larger scale reconstructions from the region.
It was found (I) that peaks in spectral ratios modelled for three-layer, one-dimensional systems corresponded with thaw depths. Around Muostakh Island in the central Laptev Sea seismic receivers were deployed on the seabed. Derived depths of the ice-bonded permafrost table were between 3.7-20.7 m ± 15 %, increasing with distance from the coast. (II) Temperatures modelled during the transition to subsea permafrost resembled isothermal conditions after about 2000 years of inundation at Cape Mamontov Klyk, consistent with observations from offshore boreholes. Stratigraphic scenarios showed that salt distribution and infiltration had a large impact on the ice saturation in the sediments. Three key factors were identified that, when changed, shifted the modelled permafrost thaw depth most strongly: bottom water temperatures, shoreline retreat rate and initial temperature before inundation. Salt transport based on diffusion and contribution from arbitrary density-driven mechanisms only accounted for about 50 % of observed thaw depths at offshore sites hundreds to thousands of years after inundation. This bias was found consistently at all three sites in the Laptev Sea region. (III) In the temperature reconstructions, distinct differences in the local temperature histories between the western Laptev Sea and the Lena Delta sites were recognized, such as a transition to warmer temperatures a century later in the western Laptev Sea as well as a peak in warming three decades later. The local permafrost surface temperature history at Sardakh Island in the Lena Delta was reminiscent of the circum-Arctic regional average trends. However, Mamontov Klyk in the western Laptev Sea was consistent to Arctic trends only in the most recent decade and was more similar to northern hemispheric mean trends. Both sites were consistent with a rapid synoptic recent warming.
In conclusion, the consistency between modelled response, expected permafrost distribution, and observational data suggests that the passive seismic method is promising for the determination of the thickness of unfrozen sediment on the continental Arctic shelf. The quantified gap between currently modelled and observed thaw depths means that the impact of degradation on climate forcing, ecosystems, and infrastructure is larger than current models predict. This discrepancy suggests the importance of further mechanisms of salt penetration and thaw that have not been considered – either pre-inundation or post-inundation, or both. In addition, any meaningful modelling of subsea permafrost would have to constrain the identified key factors and their regional differences well. The shallow permafrost boreholes provide missing well-resolved short-scale temperature information in the coastal permafrost tundra of the Arctic. As local differences from circum-Arctic reconstructions, such as later warming and higher warming magnitude, were shown to exist in this region, these results provide a basis for local surface temperature record parameterization of climate and, in particular, permafrost models. The results of this work bring us one step further to understanding the full picture of the transition from terrestrial to subsea permafrost.
Zwei grundlegende Herausforderungen der sozialen Inklusionsforschung werden im vorliegenden Beitrag erläutert: Die Operationalisierung sozialer Inklusion sowie sonderpädagogischer Förderbedarfe. Anhand der dargelegten Forschung wird untersucht, ob die beiden methodischen Aspekte zu fehlerhaften Schlüssen und widersprüchlichen Forschungsergebnissen über die soziale Inklusion von Kindern mit sonderpädagogischem Förderbedarf führen. Dementsprechend wird die Vermeidung fehlerhafter Schlüsse und widersprüchlicher Forschungsergebnisse mittels einer Optimierung der Operationalisierung sozialer Inklusion sowie sonderpädagogischer Förderbedarfe thematisiert. Die vorliegende Forschung fokussiert sich hierbei vorrangig auf die soziometrischen Methoden zur Erfassung sozialer Inklusion sowie auf schulisches Problemverhalten im Sinne des Förderbedarfs emotional-soziale Entwicklung (insbesondere internalisierende aber auch externalisierende Verhaltensprobleme).
Autour de 1990 en France et de 2005 en Allemagne, deux nouvelles catégories sont introduites dans le champ de la statistique de la population. Toutes deux, « immigré » et « Person mit Migrationshintergrund », font appel au registre de la migration pour qualifier un groupe de population. Notre analyse montre que ces deux événements sont révélateurs d’un changement de signification des catégorisations statistiques de la migration dans les deux pays, de la description de la mobilité vers l’observation de l’altérité de la population, changement lié au contexte de la politique publique dite d’« intégration » qui se développe en France et en Allemagne dans les années 1990-2000. La thèse interroge ainsi la manière dont la statistique rend la migration socialement pertinente pour construire l’altérité. Pour pouvoir comprendre le virage entrepris dans les nomenclatures statistiques et le resituer dans une perspective de longue durée, nous avons postulé qu’il fallait aller chercher dans l’histoire de la statistique ce qui avait tenu lieu de classification principale de la population, en lieu et place des nouvelles catégories inventées au tournant des XXe et XXIe siècles. Nous nous sommes donc interrogée sur la genèse et l’institutionnalisation des catégories de l’altérité et de la mobilité dans la période 1880-1914, alors que la France et l’Allemagne, à l’époque le Deutsches Kaiserreich, se constituent en États-nations et en empires coloniaux. Pour observer ces processus empiriquement, nous avons choisi de comparer les pratiques de catégorisation de l’altérité et la mobilité (1) en France et en Allemagne, (2) à deux périodes différentes, 1880-1914 et 1990-2010, et (3) dans le contexte métropolitain et colonial. L’analyse socio-historique comparée d’après la méthodologie de la comparaison en contexte a reposé sur une asymétrie assumée entre les deux périodes étudiées : tandis qu’il s’agissait de reconstruire la genèse des catégories « immigré » et « Person mit Migrationshintergrund » à deux moments distincts temporellement en France et en Allemagne, l’analyse de la période 1880-1914 a consisté à mettre au jour ruptures et continuités historiques des principes de classification sur l’ensemble de la période dans une perspective croisée. La démarche n’est ni chronologique ni rétrospective : elle contraste deux configurations historiques pour tenter d’identifier des ressemblances et des différences. Nos résultats montrent qu’entre 1880 et 1914, la catégorie de migration est majoritairement associée à un phénomène de mobilité dans les discours politiques et statistiques. À cette époque, la focale se porte sur l’émigration, redéfinie comme un déplacement géographique en dehors des frontières de la nation et de l’Empire. Le transport des « émigrants », catégorie de population qui nourrit le débat et les tableaux statistiques, fait l’objet des problématisations politiques. Les statistiques relatives à l’émigration comme mobilité étaient alors séparées de l’observation de la composition de la population, à travers le critère de la nationalité dans le contexte métropolitain et des schémas « raciaux » dans le contexte colonial. En 1990 en France et 2005 en Allemagne, le registre de la migration est mobilisé cette fois pour observer statistiquement la composition de la population. Nos résultats ont permis de mettre au jour trois principes de construction de l’altérité dans les deux pays et dans les deux périodes étudiées : un principe national, un principe colonial et un principe migratoire. La thèse développe ainsi une approche renouvelée des interactions entre observation statistique et politique publique, en testant empiriquement sur le terrain des statistiques relatives à la migration l’hypothèse de la « circularité du savoir et de l’action » mise au point par Alain Desrosières
Self-assembly and crosslinking approaches of double hydrophilic linear-brush block copolymers
(2019)
Selenite pseudomorphs
(2019)
Die Beschäftigten des französischen Uhrenherstellers LIP machten 1973 europaweit Furore: Im Kampf gegen Entlassungen stellten sie Verhandlungsroutinen und Hierarchien infrage und nahmen Produktion und Verkauf von Armbanduhren in die eigene Hand. Wenige Jahre später gründeten die »LIPs« mehrere Produktionsgenossenschaften.
Jens Beckmann untersucht diese Auseinandersetzungen von ihren Anfängen bis zum Arbeitsalltag in den 1980er Jahren. Er zeigt, welche Vorstellungen von Selbstverwaltung sich hier niederschlugen, und nimmt eine gründliche Kontextualisierung in Branche und Region vor – von der Revolte der 1968er Jahre bis zu Kurzarbeit und Sozialplänen.
In zweigliedrigen Sekundarschulsystemen mit gleicher Abschlussorientierung – wie sie in immer mehr Bundesländern zu finden sind – tritt die Einzelschule mit ihren spezifischen Eigenschaften in den Fokus der Schulwahl. Als eine der ersten Studien untersucht Anne Jurczok, welche Schuleigenschaften Eltern präferieren, welche Informationen sie nutzen und welche Einzelschulen sie unter den Bedingungen der Zweigliedrigkeit auswählen und ablehnen. Auf Grundlage werterwartungstheoretischer Überlegungen und der Frame-Selektion wird der Prozess der Einzelschulwahl konzeptualisiert und die institutionellen, lokalen und sozio-kulturellen Bedingungen der Wahlsituation berücksichtigt.
Rowdytum, ein Begriff, der im russischen Zarenreich für die Ungezogenheit niederer Schichten stand, bezeichnet heute vor allem die Gewaltexzesse von Fußballfans. In der Sowjetunion und im übrigen Ostblock war Rowdytum viel mehr: ein Sinnbild abweichenden Verhaltens, eine unscharf definierte Straftat, ein willkürliches Stigma, das jeden treffen konnte.
Matej Kotalík erforscht das Rowdytum grenzübergreifend und verfolgt dessen Geobiografie von der Sowjetunion in die CS(S)R und in die DDR, von 1956 bis 1989. Seine Bilanz ist ambivalent. Ungeachtet sowjetischer Impulse war der entsprechende Straftatbestand durch eigene Rechtstraditionen beider Länder geprägt. Als Alltagserscheinung markierte Rowdytum die Grenzen des gesellschaftlich Akzeptablen, die in den 1960er Jahren zugleich neu verhandelt wurden. Die Polizeigewalt gegen Außenseiter wandelte sich in einer individualisierten Gesellschaft zunehmend zum Streitpunkt zwischen dem Staat und seinen Bürgern.
Die vorliegende Arbeit untersucht erstmals systematisch das Gesamtwerk Roberto Bolaños mit Blick auf die vielfältigen intertextuellen Bezüge des chilenischen Autors. Posthum vor allem wegen seines Romans 2666 von der globalen Literaturkritik zum ersten Klassiker der Weltliteratur des 21. Jahrhunderts stilisiert, fungieren in Bolaños Texten intertextuelle Verweise als ein zentrales Formverfahren, das bislang von der Kritik kaum eingehender untersucht worden ist. Die Werk-Studie situiert Bolaño dabei nicht nur dezidiert innerhalb einer lateinamerikanischen Genealogie eines «wilden Lesens», sondern legt über eine Lektüre, die zugleich philologisch-detailliert und panoramatisch-ideengeschichtlich operiert, die Auseinandersetzungen von Bolaños Texten über die gescheiterten Revolutionen in Lateinamerika oder die Verheerungen des globalen Kapitalismus mit dem literarischen Kanon der (Post-)Moderne frei. Diese umfassen neben der lateinamerikanischen Literatur um Autoren wie Neruda, Borges und Parra insbesondere Bezüge auf die spanische und französische Literatur von Góngora und Pascal über Baudelaire bis zu Perec sowie auf weitere Klassiker der Moderne in Gestalt von Schriftstellern wie Ernst Jünger oder William Carlos Williams.
Weakly electric mormyrid fish comprise about 200 species. 15 species of the genus Campylomormyrus have been described. These are very diverse concerning the trunk-like snout and the shape and duration of the electric organ discharge (EOD) and the anatomy of the electric organ. In this dissertation data on the reproduction in captivity of four species and on the ontogeny of the EOD and the EO of three species are presented.
Reproduction of the four species C. compressirostris, C. rhynchophorus, C. tshokwe and C. numenius: Cyclical reproduction was provoked by changing only water conductivity (C): decreasing C led to gonadal recrudescence, an increase induced gonad regression. Data on the reproduction and development of three species are presented (in C. numenius gonad development could only be achieved in males). Agonistic behavior in the C. tshokwe pair forced us to divide the breeding tank; therefore, only ovipositions occurred. However, injection of an artificial GnRH hormone allowed us to obtain ripe eggs and sperm and to perform successful artificial reproduction. All three species (C. compressirostris, C. rhynchophorus, C. tshokwe) are indeterminate fractional spawners. Spawnings/ovipositions occurred during the second half of the night; no parental care was observed; no special spawning substrates were necessary. C. compressirostris successfully spawned in breeding groups, C. rhynchophorus as pair. Spawning intervals ranged from 6 to 66 days in C. rhynchophorus, 10–75 days in C. tshokwe, and 18 days in C. compressirostris (calculated values). Fecundities (eggs per fractional spawning) ranged from 70 to 1570 eggs in C. rhynchophorus, 100–1192 in C. tshokwe, and 38–246 in C. compressirostris. All three species produce yolky, slightly sticky eggs. Egg diameter ranges from 2.3–3.0 mm. Hatching occurred on day 3, feeding started on day 11. Transition from larval to juvenile stage occurred at around 20 mm total length (TL). At this size C. rhynchophorus developed a higher body than the two other species and differences between the species in the melanin pigmentation of the unpaired fins occurred. Between 32 and 35 mm TL the upper and lower jaws developed.
C. compressirostris and C. tamandua are similar in morphology and both produce short EODs of ca. 150-200 μs duration. Both species reproduce easily in captivity. We tried to obtain natural hybrids in two breeding groups, 1) four males of C. compressirostris and three females of C. tamandua and 2) six females of C. compressirostris and four males of C. tamandua. In both combinations several times oviposition occurred, however, we never found fertilized eggs. In subsequent experiments, not described here, we obtained hybrids between these two species by means of artificial reproduction.
Ontogeny of the EOD and the EO: The Campylomormyrus species are very diverse both concerning the shape and the duration of their EODs. There are species with very short EODs, e.g. C. compressirostris duration, a species with an EOD length of about 4-8 ms duration (C. tshokwe) and species with very long EODs of about 25 ms duration (e.g. C. rhynchophorus). Due to the successful breeding of the three species in captivity, we were able to investigate in detail the ontogeny of the EOD. Larvae of the three species C. compressirostris, C. tshokwe and C. rhynchophorus first produce a biphasic larval EOD typical for these small larvae. The first activity of the adult electric organ in the caudal peduncle is a biphasic juvenile EOD. Juvenile C. compressirostris and C. tshokwe start out with a short biphasic EOD of about 160 – 200 μs duration at sizes between 25 mm (C. compressirostris) and 37 mm (C. tshokwe). Adult C. compressirostris show an EOD identical to that of the juvenile. In C. tshokwe, the juvenile EOD changes continuously during development both concerning duration, amplitude increase and shape. 18 cm long C. tshokwe still do not yet produce an EOD typical for the adult fish. Juveniles of C. rhynchophorus produce at 33 mm total length a juvenile biphasic EOD, however, of longer duration (about 640 μs) than the two species mentioned above. This juvenile EOD changes continuously both in form, amplitude increase and duration with growth until the adult EOD waveform appears at about 15 cm body length. In juveniles about seven cm long the triphasic feature of the EOD starts to develop due to the appearance of a second head positive phase. Specific EOD stages are produced in relation to size and not to age. Individual differences in the EOD both concerning shape and duration are very small. The basic anatomy of the electrocytes is very similar in all three species: the main stalk which receives the innervation, is located at the caudal face of the electrocyte. Membrane penetrations of the stalks do not occur. However, there are differences in the fine structure of the electrocytes in the three species. Papillae, proliferations of the membrane, which increase the surface area of the electrocyte and are thought to incrase the EOD-duration, are only found in C. tshokwe and C. rhynchophorus. In these two species in addition, holes develop in the electrocytes during ontogeny. This might also have an impact on EOD duration.
STERILE APETALA (SAP) is known to be an essential regulator of flower development for over 20 years. Loss of SAP function in the model plant Arabidopsis thaliana is associated with a reduction of floral organ number, size and fertility. In accordance with the function of SAP during early flower development, its spatial expression in flowers is confined to meristematic stages and to developing ovules. However, to date, despite extensive research, the molecular function of SAP and the regulation of its spatio-temporal expression still remain elusive.
In this work, amino acid sequence analysis and homology modeling revealed that SAP belongs to the rare class of plant F-box proteins with C-terminal WD40 repeats. In opisthokonts, this type of F-box proteins constitutes the substrate binding subunit of SCF complexes, which catalyze the ubiquitination of proteins to initiate their proteasomal degradation. With LC-MS/MS-based protein complex isolation, the interaction of SAP with major SCF complex subunits was confirmed. Additionally, candidate substrate proteins, such as the growth repressor PEAPOD 1 and 2 (PPD1/2), could be revealed during early stages of flower development. Also INDOLE-3-BUTYRIC ACID RESPONSE 5 (IBR5) was identified among putative interactors. Genetic analyses indicated that, different from substrate proteins, IBR5 is required for SAP function. Protein complex isolation together with transcriptome profiling emphasized that the SCFSAP complex integrates multiple biological processes, such as proliferative growth, vascular development, hormonal signaling and reproduction. Phenotypic analysis of sap mutant and SAP overexpressing plants positively correlated SAP function with plant growth during reproductive and vegetative development.
Furthermore, to elaborate on the transcriptional regulation of SAP, publicly available ChIP-seq data of key floral homeotic proteins were reanalyzed. Here, it was shown that the MADS-domain transcription factors APETALA 1 (AP1), APETALA 3 (AP3), PISTILLATA (PI), AGAMOUS (AG) and SEPALLATA 3 (SEP3) bind to the SAP locus, which indicates that SAP is expressed in a floral organ-specific manner. Reporter gene analyses in combination with CRISPR/Cas9-mediated deletion of putative regulatory regions further demonstrated that the intron contains major regulatory elements of SAP in Arabidopsis thaliana.
In conclusion, these data indicate that SAP is a pleiotropic developmental regulator that acts through tissue-specific destabilization of proteins. The presumed transcriptional regulation of SAP by the floral MADS-domain transcription factors could provide a missing link between the specification of floral organ identity and floral organ growth pathways.
Mouse aldehyde oxidases (mAOXs) have a homodimeric structure and belong to xanthine oxidase family of molybdo-flavoenzymes. In general, each dimer is characterized by three subdomains: a 20 kDa N-terminal 2x[2Fe2S] cluster containing domain, a 40 kDa central FAD-containing domain and an 85 kDa C-terminal molybdenum cofactor (Moco) containing domain. Aldehyde oxidases have a broad substrate specificity including the oxidation of different aldehydes and N-heterocyclic compounds. AOX enzymes are present in mainly all eukaryotes. Four different homologs of AOX were identified to be present with varying numbers among species and rodents like mice and rats contain the highest number of AOX isoenzymes. There are four identified homologs in mouse named mAOX1, mAOX3, mAOX2, and mAOX4. The AOX homologs in mice are expressed in a tissue-specific manner. Expression of mAOX1 and mAOX3 are almost superimposable and predominantly synthesized in liver, lung, and testis. The richest source of mAOX4 is the Harderian gland, which is found within the eye's orbit in tetrapods. Expression of mAOX2 is strictly restricted to the Bowman’s gland, the main secretory organ of the nasal mucosa.
In this study, the four catalytically active mAOX enzymes were expressed in a heterologous expression system in Escherichia coli and purified in a catalytically active form. Thirty different structurally related aromatic, aliphatic and N-heterocyclic compounds were used as substrates, and the kinetic parameters of all four mAOX enzymes were directly compared. The results showed that all enzymes can catalyze a broad range of substrates. Generally, no major differences between mAOX1, mAOX3 and mAOX2 were identified and the substrate specificity of mAOX1, mAOX3, and mAOX2 was broader compared to that of mAOX4 since mAOX4 showed no activity with substrates like methoxy-benzaldehydes, phenanthridine, N1-methyl-nicotinamide, and cinnamaldehyde and 4-(dimethylamino)cinnamaldehyde.
We investigated differences at the flavin site of the mAOX enzymes by measuring the ability of the four mAOX enzymes to oxidize NADH in the absence of oxygen. NADH was able to reduce only mAOX3. The four mouse AOXs are also characterized by quantitative differences in their ability to produce superoxide radicals. mAOX2 is the enzyme generating the largest rate of superoxide radicals of around 40% in relation to moles of substrate converted and it is followed by mAOX1 with a ratio of 30%.
To understand the factors that contribute to the substrate specificity of mAOX4, site-directed mutagenesis was applied to substitute amino acids in the substrate-binding funnel by the ones present in mAOX1, mAOX3, and mAOX2. The amino acids Val1016, Ile1018 and Met1088 were selected as targets. An increase in activity was obtained by the amino acid exchange M1088V in the active site identified to be specific for mAOX4, to the amino acid identified in mAOX3.
Alexander Rhode investigates performance-oriented measures of Contracting Authorities in public tenders conducted within the EU. He finds that Contracting Authorities can improve their performance and attract more suppliers by publishing (as precise as possible) starting prices in the beginning of a tender. First, he reports that compared with private-sector negotiations, starting prices do not create entry barriers in public procurement. Second, he finds that increased numerical precision of starting prices is linearly correlated with better performance and a higher number of bids. In public procurement, suppliers tend to attribute increased credibility to precise starting prices which reduces their (perceived) entry risks.
Pillars of Salt
(2019)
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.
Parlamentarier als Beruf
(2019)
Die politische Professionalisierung hat innerhalb der institutionellen Rahmenbedingungen zur Sozialfigur des Berufspolitikers geführt. Diese Entwicklung wird im theoretischen Teil der Arbeit hergeleitet und im empirischen Teil mit umfangreichen Daten belegt. Bemerkenswert ist, dass es dabei nicht zu erheblichen Veränderungen in den Rekrutierungsmustern und Karriereverläufen der Abgeordneten gekommen ist. Vielmehr erweisen sich die von Dietrich Herzog herausgearbeiteten Karrieretypen auch heute noch als gültig und mussten nur moderat angepasst werden. Es zeigt sich damit eine erstaunliche Kontinuität in der politischen Elitenbildung. Die in Deutschland sehr gefestigten institutionellen Rahmenbedingungen, die den Zugang und die Attraktivität politischer Karrieren determinieren, haben offensichtlich auch zu einer Stabilisierung der Karrieretypen geführt.
Collagen is the most abundant protein in mammals. In many tissues, collagen molecules assemble to form a hierarchical structure. In the smallest supramolecular unit, named fibril, each molecule is displaced in the axial direction with respect to its neighbors. This staggering creates a periodic gap and overlap regions, where the gap regions exhibit 20% less density. These fibril-forming collagens play an essential role in the strength of connective tissues. Despite much effort, directed at understanding collagen function and regulation, the influence of the chemical environment on the local structural and mechanical properties remains poorly understood. Recent studies, aimed at elucidating the effect of osmotic pressure, showed that collagen contracts upon water removal. This observation highlights the importance of water for the stabilization and mechanics of the collagen molecule.
Using collagen mimetic peptides (CMPs), which fold into triple helical structures reminiscent of natural collagen, the primary goal of this work was to investigate the effect of the osmotic pressure on specific collagen-mimetic sequences. CMPs were used as the model system as they provide sequence control, which is essential for discriminating local from global structural changes and for relating the observed effects to existing knowledge about the full-length collagen molecule. Of specific interest was the structure of individual collagen triple helices as well as their organization into self-assembled higher order structures. These key structural features were monitored with infrared spectroscopy (IR) and synchrotron X-ray scattering, while varying the osmotic pressure. For controlling the osmotic pressure, CMP powder samples were incubated in air of defined relative humidity, ranging from dry conditions to highly “humid”. In addition, to obtain more biologically relevant conditions, the CMPs were measured in ultrapure water and in solutions containing small molecule osmolytes.
Using the sequences (Pro-Pro-Gly)10, (Pro-Hyp-Gly)10 and (Hyp-Hyp-Gly)10, it was shown that CMPs with different degrees of proline hydroxylation (Hyp = hydroxyproline) exhibit a sequence-specific response to osmotic pressure. IR spectroscopy revealed that osmotic pressure changes affect the strength of the triple helix stabilizing, interchain hydrogen bond and that the extent of this change depends on the degree of hydroxylation. X-ray scattering experiments further showed that changes in osmotic pressure affect both the molecular length as well as the higher order organization of CMPs. Starting from a pseudo-hexagonal packing in the dry state, all three CMPs showed isotropic swelling when increasing the water content to approximately 1.2 water molecules per amino acid, again to different extents depending on the degree of hydroxylation. When increasing the water content further, this pseudo-hexagonal arrangement breaks down. In the fully hydrated state, each CMP is characterized by its own specific and more complex packing geometry.
While these changes in the lateral packing arrangement suggest swelling upon hydration, an overall decrease of the molecular length (i.e. contraction) was observed in the axial direction. Also for this structural feature, a strong dependency on the specific amino acid sequence was found. Interestingly, the observed contraction is the opposite of what has been reported for natural collagen. As (Pro-Pro-Gly)n, (Pro-Hyp-Gly)n and (Hyp-Hyp-Gly)n repeat units are found in collagen with a relatively high abundance, this suggests that other collagen sequence fragments need to respond to hydration in the opposite way to obtain a net elongation of the full-length collagen molecule.
To test this hypothesis, sequences predicted to be sensitive to osmotic pressure were considered. One such sequence, consisting of two repeat units (Ala-Arg-Gly-Ser-Asp-Gly), was inserted as a guest into a (Pro-Pro-Gly) host. When compared to the canonical CMP sequences investigated earlier, the lateral helix packing follows a similar trend with increasing hydration; however, the host-guest CMP axially elongates with increasing water content. This behavior is more similar to what has been found for natural collagen and suggests that different sequences do determine the molecular length of collagen sequences differently. Interestingly, the canonical sequences are more abundant in the overlap region while the guest sequence is found in the gap region. This allows to speculate that sequences in the gap and overlap regions possess a specifically fine-tuned local response to osmotic pressure changes. Clearly, more experiments with additional sequences are needed to confirm this.
In conclusion, the results obtained in this work indicate a highly sequence specific interaction between collagen and water. Osmotic pressure-induced conformational changes mostly originate from local geometries and bonding patterns and affect both the structure of individual triple helices as well as higher order assemblies. One key remaining question is how these conformational changes affect the local mechanical properties of the collagen molecule. As a first step, the stiffness (persistence length) of full-length collagen was determined using atomic force microscopy. In the future, experimental strategies need to be developed that allow for investigating the mechanical properties of specific collagen sequences, e.g. performing single-molecule force spectroscopy of CMPs.
On being and belonging
(2019)