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This cumulative doctoral dissertation, based on three publications, is devoted to the investigation of several aspects of azobenzene molecular switches, with the aid of computational chemistry.
In the first paper, the isomerization rates of a thermal cis → trans isomerization of azobenzenes for species formed upon an integer electron transfer, i.e., with added or removed electron, are calculated from Eyring’s transition state theory and activation energy barriers, computed by means of density functional theory. The obtained results are discussed in connection with an experimental study of the thermal cis → trans isomerization of azobenzene derivatives in the presence of gold nanoparticles, which is demonstrated to be greatly accelerated in comparison to the same isomerization reaction in the absence of nanoparticles.
The second paper is concerned with electronically excited states of (i) dimers, composed of two photoswitchable units placed closely side-by-side, as well as (ii) monomers and dimers adsorbed on a silicon cluster. A variety of quantum chemistry methods, capable of calculating molecular electronic absorption spectra, based on density functional and wave function theories, is employed to quantify changes in optical absorption upon dimerization and covalent grafting to a surface. Specifically, the exciton (Davydov) splitting between states of interest is determined from first-principles calculations with the help of natural transition orbital analysis, allowing for insight into the nature of excited states.
In the third paper, nonadiabatic molecular dynamics with trajectory surface hopping is applied to model the photoisomerization of azobenzene dimers, (i) for the isolated case (exhibiting the exciton coupling between two molecules) as well as (ii) for the constrained case (providing the van der Waals interaction with environment in addition to the exciton coupling between two monomers). For the latter, the additional azobenzene molecules, surrounding the dimer, are introduced, mimicking a densely packed self-assembled monolayer. From obtained results it is concluded that the isolated dimer is capable of isomerization likewise the monomer, whereas the steric hindrance considerably suppresses trans → cis photoisomerization.
Furthermore, the present dissertation comprises the general introduction describing the main features of the azobenzene photoswitch and objectives of this work, theoretical basis of the employed methods, and discussion of gained findings in the light of existing literature. Also, additional results on (i) activation parameters of the thermal cis → trans isomerization of azobenzenes, (ii) an approximate scheme to account for anharmonicity of molecular vibrations in calculation of the activation entropy, as well as (iii) absorption spectra of photoswitch–silicon composites obtained from time-demanding wave function-based methods are presented.
Didovets, Iulii ; Lobanova, Anastasia ; Bronstert, Axel ; Snizhko, Sergiy ; Maule, Cathrine Fox ; Krysanova, Valentina
The information about climate change impact on river discharge is vitally important for planning adaptation measures. The future changes can affect different water-related sectors. The main goal of this study was to investigate the potential water resource changes in Ukraine, focusing on three mesoscale river catchments (Teteriv, UpperWestern Bug, and Samara) characteristic for different geographical zones. The catchment scale watershed model—Soil and Water Integrated Model (SWIM)—was setup, calibrated, and validated for the three catchments under consideration. A set of seven GCM-RCM (General Circulation Model-Regional Climate Model) coupled climate scenarios corresponding to RCPs (Representative Concentration Pathways) 4.5 and 8.5 were used to drive the hydrological catchment model. The climate projections, used in the study, were considered as three combinations of low, intermediate, and high end scenarios. Our results indicate the shifts in the seasonal distribution of runoff in all three catchments. The spring high flow occurs earlier as a result of temperature increases and earlier snowmelt. The fairly robust trend is an increase in river discharge in the winter season, and most of the scenarios show a potential decrease in river discharge in the spring.
Didovets, Iulii ; Lobanova, Anastasia ; Bronstert, Axel ; Snizhko, Sergiy ; Maule, Cathrine Fox ; Krysanova, Valentina
The information about climate change impact on river discharge is vitally important for planning adaptation measures. The future changes can affect different water-related sectors. The main goal of this study was to investigate the potential water resource changes in Ukraine, focusing on three mesoscale river catchments (Teteriv, UpperWestern Bug, and Samara) characteristic for different geographical zones. The catchment scale watershed model—Soil and Water Integrated Model (SWIM)—was setup, calibrated, and validated for the three catchments under consideration. A set of seven GCM-RCM (General Circulation Model-Regional Climate Model) coupled climate scenarios corresponding to RCPs (Representative Concentration Pathways) 4.5 and 8.5 were used to drive the hydrological catchment model. The climate projections, used in the study, were considered as three combinations of low, intermediate, and high end scenarios. Our results indicate the shifts in the seasonal distribution of runoff in all three catchments. The spring high flow occurs earlier as a result of temperature increases and earlier snowmelt. The fairly robust trend is an increase in river discharge in the winter season, and most of the scenarios show a potential decrease in river discharge in the spring.
Background
Back pain patients (BPP) show delayed muscle onset, increased co-contractions, and variability as response to quasi-static sudden trunk loading in comparison to healthy controls (H). However, it is unclear whether these results can validly be transferred to suddenly applied walking perturbations, an automated but more functional and complex movement pattern. There is an evident need to develop research-based strategies for the rehabilitation of back pain. Therefore, the investigation of differences in trunk stability between H and BPP in functional movements is of primary interest in order to define suitable intervention regimes. The purpose of this study was to analyse neuromuscular reflex activity as well as three-dimensional trunk kinematics between H and BPP during walking perturbations.
Methods
Eighty H (31m/49f;29±9yrs;174±10cm;71±13kg) and 14 BPP (6m/8f;30±8yrs;171±10cm;67±14kg) walked (1m/s) on a split-belt treadmill while 15 right-sided perturbations (belt decelerating, 40m/s2, 50ms duration; 200ms after heel contact) were randomly applied. Trunk muscle activity was assessed using a 12-lead EMG set-up. Trunk kinematics were measured using a 3-segment-model consisting of 12 markers (upper thoracic (UTA), lower thoracic (LTA), lumbar area (LA)). EMG-RMS ([%],0-200ms after perturbation) was calculated and normalized to the RMS of unperturbed gait. Latency (TON;ms) and time to maximum activity (TMAX;ms) were analysed. Total motion amplitude (ROM;[°]) and mean angle (Amean;[°]) for extension-flexion, lateral flexion and rotation were calculated (whole stride cycle; 0-200ms after perturbation) for each of the three segments during unperturbed and perturbed gait. For ROM only, perturbed was normalized to unperturbed step [%] for the whole stride as well as the 200ms after perturbation. Data were analysed descriptively followed by a student´s t-test to account for group differences. Co-contraction was analyzed between ventral and dorsal muscles (V:R) as well as side right:side left ratio (Sright:Sleft). The coefficient of variation (CV;%) was calculated (EMG-RMS;ROM) to evaluate variability between the 15 perturbations for all groups. With respect to unequal distribution of participants to groups, an additional matched-group analysis was conducted. Fourteen healthy controls out of group H were sex-, age- and anthropometrically matched (group Hmatched) to the BPP.
Results
No group differences were observed for EMG-RMS or CV analysis (EMG/ROM) (p>0.025). Co-contraction analysis revealed no differences for V:R and Srigth:Sleft between the groups (p>0.025). BPP showed an increased TON and TMAX, being significant for Mm. rectus abdominus (p = 0.019) and erector spinae T9/L3 (p = 0.005/p = 0.015). ROM analysis over the unperturbed stride cycle revealed no differences between groups (p>0.025). Normalization of perturbed to unperturbed step lead to significant differences for the lumbar segment (LA) in lateral flexion with BPP showing higher normalized ROM compared to Hmatched (p = 0.02). BPP showed a significant higher flexed posture (UTA (p = 0.02); LTA (p = 0.004)) during normal walking (Amean). Trunk posture (Amean) during perturbation showed higher trunk extension values in LTA segments for H/Hmatched compared to BPP (p = 0.003). Matched group (BPP vs. Hmatched) analysis did not show any systematic changes of all results between groups.
Conclusion
BPP present impaired muscle response times and trunk posture, especially in the sagittal and transversal planes, compared to H. This could indicate reduced trunk stability and higher loading during gait perturbations.
Background
Back pain patients (BPP) show delayed muscle onset, increased co-contractions, and variability as response to quasi-static sudden trunk loading in comparison to healthy controls (H). However, it is unclear whether these results can validly be transferred to suddenly applied walking perturbations, an automated but more functional and complex movement pattern. There is an evident need to develop research-based strategies for the rehabilitation of back pain. Therefore, the investigation of differences in trunk stability between H and BPP in functional movements is of primary interest in order to define suitable intervention regimes. The purpose of this study was to analyse neuromuscular reflex activity as well as three-dimensional trunk kinematics between H and BPP during walking perturbations.
Methods
Eighty H (31m/49f;29±9yrs;174±10cm;71±13kg) and 14 BPP (6m/8f;30±8yrs;171±10cm;67±14kg) walked (1m/s) on a split-belt treadmill while 15 right-sided perturbations (belt decelerating, 40m/s2, 50ms duration; 200ms after heel contact) were randomly applied. Trunk muscle activity was assessed using a 12-lead EMG set-up. Trunk kinematics were measured using a 3-segment-model consisting of 12 markers (upper thoracic (UTA), lower thoracic (LTA), lumbar area (LA)). EMG-RMS ([%],0-200ms after perturbation) was calculated and normalized to the RMS of unperturbed gait. Latency (TON;ms) and time to maximum activity (TMAX;ms) were analysed. Total motion amplitude (ROM;[°]) and mean angle (Amean;[°]) for extension-flexion, lateral flexion and rotation were calculated (whole stride cycle; 0-200ms after perturbation) for each of the three segments during unperturbed and perturbed gait. For ROM only, perturbed was normalized to unperturbed step [%] for the whole stride as well as the 200ms after perturbation. Data were analysed descriptively followed by a student´s t-test to account for group differences. Co-contraction was analyzed between ventral and dorsal muscles (V:R) as well as side right:side left ratio (Sright:Sleft). The coefficient of variation (CV;%) was calculated (EMG-RMS;ROM) to evaluate variability between the 15 perturbations for all groups. With respect to unequal distribution of participants to groups, an additional matched-group analysis was conducted. Fourteen healthy controls out of group H were sex-, age- and anthropometrically matched (group Hmatched) to the BPP.
Results
No group differences were observed for EMG-RMS or CV analysis (EMG/ROM) (p>0.025). Co-contraction analysis revealed no differences for V:R and Srigth:Sleft between the groups (p>0.025). BPP showed an increased TON and TMAX, being significant for Mm. rectus abdominus (p = 0.019) and erector spinae T9/L3 (p = 0.005/p = 0.015). ROM analysis over the unperturbed stride cycle revealed no differences between groups (p>0.025). Normalization of perturbed to unperturbed step lead to significant differences for the lumbar segment (LA) in lateral flexion with BPP showing higher normalized ROM compared to Hmatched (p = 0.02). BPP showed a significant higher flexed posture (UTA (p = 0.02); LTA (p = 0.004)) during normal walking (Amean). Trunk posture (Amean) during perturbation showed higher trunk extension values in LTA segments for H/Hmatched compared to BPP (p = 0.003). Matched group (BPP vs. Hmatched) analysis did not show any systematic changes of all results between groups.
Conclusion
BPP present impaired muscle response times and trunk posture, especially in the sagittal and transversal planes, compared to H. This could indicate reduced trunk stability and higher loading during gait perturbations.
Ebke, Thomas ; Zanfi, Caterina ; Krüger, Hans-Peter ; Sommer, Christian ; Viennet, Thomas ; Johannßen, Dennis ; Balzaretti, Ugo ; Toussaint Ondoua, Hervé ; Agard, Olivier ; Henckmann, Wolfhart ; Simonotti, Edoardo ; Hand, Annika ; Tavakkoli, Amirpasha ; Hackbarth, Daniel ; Edinger, Sebastian ; Schollmeyer, Justus ; von Kalckreuth, Moritz Alexander ; Schmieg, Gregor ; Batista Rates, Bruno ; Kressmann, Philipp ; Hilt, Annette ; van Buuren, Jasper ; Keusch, Juliane ; Guzun, Mădălina ; Bruff, Kyla ; Stahl, Marion ; Held, Lukas
In der Philosophie des 20. Jahrhunderts wird deutlich, dass es in Frankreich und in Deutschland voneinander abweichende Sichtweisen auf die Frage gibt, ob der Mensch eine "Sonderstellung" in der Dynamik des biologischen und geschichtlichen Lebens genießt. Während sich in Deutschland die Tradition eines anthropologischen Denkens neu formiert, ist in Frankreich eine scharfe Skepsis gegenüber dem Erbe des Humanismus charakteristisch. Die Beiträge dieses zweisprachigen Buches untersuchen diese deutsch-französische Konstellation von Fragen und Autoren, und aktualisieren die Reflexion auf die (Grenzen der) Singularität des Menschen.
Im Werk des jüdischen Schriftstellers Albert Cohen (1895-1981) tritt der Liebesbegriff in all seiner schillernden Ambivalenz und Komplexität in einen kontinuierlichen Dialog mit dem ethischen Diskurs des Judentums. Die Studie macht dieses Beziehungsgeflecht zur Grundlage ihrer Reflexion und entwirft vor dem geistigen Hintergrund des Judentums eine Gesamtschau auf die bei Albert Cohen allgegenwärtigen Erscheinungsformen der Liebe. Aus diesem Blickwinkel gedeutet ergeben die im Schreiben des Autors vielschichtig entfalteten zwischenmenschlichen Beziehungsmuster eine ethische Matrix, die den (alt)jüdischen Wissens- und Erfahrungsschatz mit den Herausforderungen der Gegenwart konfrontiert und beides zueinander in Beziehung treten lässt. Jenseits dichotomischer Zuschreibungen stellt die vorliegende Monographie Albert Cohen als einen Literaten vor, dessen Leben und Wirken entlang der Kontaktzonen zwischen Orient und Okzident, zwischen Judentum und Christentum, zwischen Jüdisch-Partikularem und Kulturübergreifend-Universalem ausgerichtet war
Bei der Autorin Judith Hermann handelt es sich um eine sehr resonanzträchtige Autorin, der in der Vergangenheit eine phänomenale Aufmerksamkeit zuteil wurde und die es schaffte, sich erfolgreich auf dem Marktplatz Literatur zu positionieren und zur Bestsellerautorin zu avancieren.
Die vorliegende Studie verfolgt das Ziel, der Marke Judith Hermann auf die Spur zu kommen und die höchst unterschiedlichen Facetten der Erfolgsgeschichte zu rekonstruieren.
Juliane Witzke analysiert dazu detailliert die peri- und epitextuellen Praktiken der Jahre 1998 bis 2014 und bezieht sich dabei auf die Paratexte der ersten vier Werke der Autorin. Ergänzt werden diese Begleittexte durch eine Analyse der Bild- und Tondokumente sowie der Buchpreisverleihungen. Die grundlegende Frage lautet: Wie ist der Wandel der Inszenierungspraktiken gestaltet? Des Weiteren gibt die Arbeit – anhand von 100 Büchern der Gegenwart – Aufschluss über Strategien der Lektürelenkung der letzten 16 Jahre.
Die Naturphilosophie und die Politische Philosophie werden gemeinhin als Disziplinen aufgefasst, die grundlegend verschiedene Problembereiche zum Gegenstand haben. Die Aporien zu überwinden, welche daraus resultieren, ist die Pointe von Plessners Philosophischer Anthropologie.
In dieser Studie wird gezeigt, wie Plessner in der Aneignung elementarer Topoi der klassischen Ontologie eine strukturell neuartige "Ontologie des Organischen" entwickelt. Dieser von Plessner beiläufig verwendete Ausdruck wird in dieser Studie systematisch entwickelt. Was dabei elaboriert wird, ist eine komplexe naturphilosophische "Ontologie des Ausgleichs". In dieser Ontologie des Ausgleichs werden elementare naturphilosophische Ausgleichsleistungen expliziert, die als solche einen Doppelsinn haben: was auf der organismischen Ebene strukturell als Ausgleich des organischen Körpers mit sich selbst und der Umwelt expliziert wird, nimmt im menschlichen Bereich die Gestalt einer Ontologie der Personen an, wo die strukturell identische Ausgleichsleistung als das Spiel der Personalisierung zu vollziehen ist.
Plessners Ansatz wird hier als ein auf diese Fragen neuartig antwortender, gleichberechtigt als ontologischer und sozialphilosophischer Ansatz expliziert.
Durch Art. 20 Abs. 1 des Grundgesetzes wird die Bundesrepublik Deutschland als demokratischer und sozialer Bundesstaat insbesondere dem Föderalismus verpflichtet. Er ist neben der Demokratie eine der Säulen unseres Staatswesens. Im Bewusstsein dieser Grundentscheidung unserer Verfassung fällt mit Art. 115f Abs. 1 Nr. 2 GG eine Vorschrift auf, die hiervon im Verteidigungsfall eine weitreichende Ausnahme zu ermöglichen scheint. Die Bundesregierung soll dann unter bestimmten Voraussetzungen außer der Bundesverwaltung auch den Landesregierungen und Landesbehörden Weisungen erteilen können. Es stellt sich in Anbetracht eines solchen Ausnahmerechts die Frage, wie sich dieses Weisungsrecht der Bundesregierung in unser Rechtssystem einfügt.
Der Autor nähert sich dieser Frage zunächst über die geschichtlichen Hintergründe, die zur Einfügung der Vorschrift geführt haben. Er geht detailliert auf die Voraussetzungen dieses Weisungsrechts der Bundesregierung ein und stellt es in seinen systematischen Zusammenhang. Neben einer Darstellung des Weisungsbegriffs als Möglichkeit der Einflussnahme auf die Bundesverwaltung und die Länder, werden auch die damit umschriebenen Weisungsadressaten näher untersucht. Auch den Fragen, welchen Gegenstand Weisungen nach dieser Vorschrift haben können, wie sie zu erlassen sind und welche Wirkungen sich aus ihnen ergeben, wird in der Untersuchung detailreich nachgegangen. Daneben behandelt der Autor die sich daraus ergebenden Anschlussfragen, welcher Rechtsschutz gegen derartige Weisungen besteht, wer damit verbundene Aufgaben zu finanzieren hat und wer für eventuelle Schäden zu haften hat. Das Werk schließt mit einer Erörterung, ob es sich bei dieser Vorschrift um eine verfassungswidrige Verfassungsnorm handelt, und einem Blick auf internationale Vorschriften, die Einfluss auf das Weisungsrecht nehmen könnten.
Um den zunehmenden Diebstahl digitaler Identitäten zu bekämpfen, gibt es bereits mehr als ein Dutzend Technologien. Sie sind, vor allem bei der Authentifizierung per Passwort, mit spezifischen Nachteilen behaftet, haben andererseits aber auch jeweils besondere Vorteile. Wie solche Kommunikationsstandards und -Protokolle wirkungsvoll miteinander kombiniert werden können, um dadurch mehr Sicherheit zu erreichen, haben die Autoren dieser Studie analysiert. Sie sprechen sich für neuartige Identitätsmanagement-Systeme aus, die sich flexibel auf verschiedene Rollen eines einzelnen Nutzers einstellen können und bequemer zu nutzen sind als bisherige Verfahren. Als ersten Schritt auf dem Weg hin zu einer solchen Identitätsmanagement-Plattform beschreiben sie die Möglichkeiten einer Analyse, die sich auf das individuelle Verhalten eines Nutzers oder einer Sache stützt.
Ausgewertet werden dabei Sensordaten mobiler Geräte, welche die Nutzer häufig bei sich tragen und umfassend einsetzen, also z.B. internetfähige Mobiltelefone, Fitness-Tracker und Smart Watches. Die Wissenschaftler beschreiben, wie solche Kleincomputer allein z.B. anhand der Analyse von Bewegungsmustern, Positionsund Netzverbindungsdaten kontinuierlich ein „Vertrauens-Niveau“ errechnen können. Mit diesem ermittelten „Trust Level“ kann jedes Gerät ständig die Wahrscheinlichkeit angeben, mit der sein aktueller Benutzer auch der tatsächliche Besitzer ist, dessen typische Verhaltensmuster es genauestens „kennt“.
Wenn der aktuelle Wert des Vertrauens-Niveaus (nicht aber die biometrischen Einzeldaten) an eine externe Instanz wie einen Identitätsprovider übermittelt wird, kann dieser das Trust Level allen Diensten bereitstellen, welche der Anwender nutzt und darüber informieren will. Jeder Dienst ist in der Lage, selbst festzulegen, von welchem Vertrauens-Niveau an er einen Nutzer als authentifiziert ansieht. Erfährt er von einem unter das Limit gesunkenen Trust Level, kann der Identitätsprovider seine Nutzung und die anderer Services verweigern.
Die besonderen Vorteile dieses Identitätsmanagement-Ansatzes liegen darin, dass er keine spezifische und teure Hardware benötigt, um spezifische Daten auszuwerten, sondern lediglich Smartphones und so genannte Wearables. Selbst Dinge wie Maschinen, die Daten über ihr eigenes Verhalten per Sensor-Chip ins Internet funken, können einbezogen werden. Die Daten werden kontinuierlich im Hintergrund erhoben, ohne dass sich jemand darum kümmern muss. Sie sind nur für die Berechnung eines Wahrscheinlichkeits-Messwerts von Belang und verlassen niemals das Gerät. Meldet sich ein Internetnutzer bei einem Dienst an, muss er sich nicht zunächst an ein vorher festgelegtes Geheimnis – z.B. ein Passwort – erinnern, sondern braucht nur die Weitergabe seines aktuellen Vertrauens-Wertes mit einem „OK“ freizugeben.
Ändert sich das Nutzungsverhalten – etwa durch andere Bewegungen oder andere Orte des Einloggens ins Internet als die üblichen – wird dies schnell erkannt. Unbefugten kann dann sofort der Zugang zum Smartphone oder zu Internetdiensten gesperrt werden. Künftig kann die Auswertung von Verhaltens-Faktoren noch erweitert werden, indem z.B. Routinen an Werktagen, an Wochenenden oder im Urlaub erfasst werden. Der Vergleich mit den live erhobenen Daten zeigt dann an, ob das Verhalten in das übliche Muster passt, der Benutzer also mit höchster Wahrscheinlichkeit auch der ausgewiesene Besitzer des Geräts ist.
Über die Techniken des Managements digitaler Identitäten und die damit verbundenen Herausforderungen gibt diese Studie einen umfassenden Überblick. Sie beschreibt zunächst, welche Arten von Angriffen es gibt, durch die digitale Identitäten gestohlen werden können. Sodann werden die unterschiedlichen Verfahren von Identitätsnachweisen vorgestellt. Schließlich liefert die Studie noch eine zusammenfassende Übersicht über die 15 wichtigsten Protokolle und technischen Standards für die Kommunikation zwischen den drei beteiligten Akteuren: Service Provider/Dienstanbieter, Identitätsprovider und Nutzer. Abschließend wird aktuelle Forschung des Hasso-Plattner-Instituts zum Identitätsmanagement vorgestellt.
Via their powerful radiation, stellar winds, and supernova explosions, massive stars (Mini & 8 M☉) bear a tremendous impact on galactic evolution. It became clear in recent decades that the majority of massive stars reside in binary systems. This thesis sets as a goal to quantify the impact of binarity (i.e., the presence of a companion star) on massive stars. For this purpose, massive binary systems in the Local Group, including OB-type binaries, high mass X-ray binaries (HMXBs), and Wolf-Rayet (WR) binaries, were investigated by means of spectral, orbital, and evolutionary analyses.
The spectral analyses were performed with the non-local thermodynamic equillibrium (non-LTE) Potsdam Wolf-Rayet (PoWR) model atmosphere code. Thanks to critical updates in the calculation of the hydrostatic layers, the code became a state-of-the-art tool applicable for all types of hot massive stars (Chapter 2). The eclipsing OB-type triple system δ Ori served as an intriguing test-case for the new version of the PoWR code, and provided key insights regarding the formation of X-rays in massive stars (Chapter 3). We further analyzed two prototypical HMXBs, Vela X-1 and IGR J17544-2619, and obtained fundamental conclusions regarding the dichotomy of two basic classes of HMXBs (Chapter 4). We performed an exhaustive analysis of the binary R 145 in the Large Magellanic Cloud (LMC), which was claimed to host the most massive stars known. We were able to disentangle the spectrum of the system, and performed an orbital, polarimetric, and spectral analysis, as well as an analysis of the wind-wind collision region. The true masses of the binary components turned out to be significantly lower than suggested, impacting our understanding of the initial mass function and stellar evolution at low metallicity (Chapter 5). Finally, all known WR binaries in the Small Magellanic Cloud (SMC) were analyzed. Although it was theoretical predicted that virtually all WR stars in the SMC should be formed via mass-transfer in binaries, we find that binarity was not important for the formation of the known WR stars in the SMC, implying a strong discrepancy between theory and observations (Chapter 6).
Das Buch bietet eine systematische Erklärung der bisher wenig beachteten Phänomene von Wandel und Stabilität legislativer Vetopunkte (VP) in parlamentarischen Demokratien.
Theoretisch ermöglichen die gemeinsame Betrachtung der Akteursstrategien auf Gesetzgebungs- und Reformebene und deren gegenseitige Beeinflussung die Identifikation institutioneller Gleichgewichte. Die Erklärung der Autorin betont die Bedeutung der Mehrheiten beschränkenden Wirkung von Vetoinstitutionen für die Reformpräferenzen der Akteure. Im Reformprozess wird die Legitimität der Vetopunkte als wesentlicher Faktor angenommen. Sie beeinflusst Kosten und Nutzen der Akteure durch eine potenzielle elektorale Bestrafung von Versuchen, legitime Vetopunkte zu schwächen bzw. illegitime Vetopunkte zu bewahren.
Empirisch wird die Erklärung mittels einer QCA–Analyse für 38 etablierte parlamentarische Demokratien sowie anhand vertiefender Fallstudien zur Entwicklung der Vetoinstitutionen in fünf Ländern überprüft.
Culture-driven innovation
(2017)
This cumulative dissertation deals with the potential of underexplored cultural sources for innovation.
Nowadays, firms recognize an increasing demand for innovation to keep pace with an ever-growing dynamic worldwide competition. Knowledge is one of the most crucial sources and resource, while until now innovation has been foremost driven by technology. But since the last years, we have been witnessing a change from technology's role as a driver of innovation to an enabler of innovation. Innovative products and services increasingly differentiate through emotional qualities and user experience. These experiences are hard to grasp and require alignment in innovation management theory and practice.
This work cares about culture in a broader matter as a source for innovation. It investigates the requirements and fundamentals for "culture-driven innovation" by studying where and how to unlock cultural sources. The research questions are the following: What are cultural sources for knowledge and innovation? Where can one find cultural sources and how to tap into them?
The dissertation starts with an overview of its central terms and introduces cultural theories as an overarching frame to study cultural sources for innovation systematically. Here, knowledge is not understood as something an organization owns like a material resource, but it is seen as something created and taking place in practices. Such a practice theoretical lens inheres the rejection of the traditional economic depiction of the rational Homo Oeconomicus. Nevertheless, it also rejects the idea of the Homo Sociologicus about the strong impact of society and its values on individual actions. Practice theory approaches take account of both concepts by underscoring the dualism of individual (agency, micro-level) and structure (society, macro-level). Following this, organizations are no enclosed entities but embedded within their socio-cultural environment, which shapes them and is also shaped by them.
Then, the first article of this dissertation acknowledges a methodological stance of this dualism by discussing how mixed methods support an integrated approach to study the micro- and macro-level. The article focuses on networks (thus communities) as a central research unit within studies of entrepreneurship and innovation.
The second article contains a network analysis and depicts communities as central loci for cultural sources and knowledge. With data from the platform Meetup.com about events etc., the study explores which overarching communities and themes have been evolved in Berlin's start up and tech scene.
While the latter study was about where to find new cultural sources, the last article addresses how to unlock such knowledge sources. It develops the concept of a cultural absorptive capacity, that is the capability of organizations to open up towards cultural sources. Furthermore, the article points to the role of knowledge intermediaries in the early phases of knowledge acquisition. Two case studies on companies working with artists illustrate the roles of such intermediaries and how they support firms to gain knowledge from cultural sources.
Overall, this dissertation contributes to a better understanding of culture as a source for innovation from a theoretical, methodological, and practitioners' point of view. It provides basic research to unlock the potential of such new knowledge sources for companies - sources that so far have been neglected in innovation management.
Lignin valorization
(2017)
The topic of this project is the use of lignin as alternative source of aromatic building blocks and oligomers to fossil feedstocks. Lignin is known as the most abundant aromatic polymer in nature and is isolated from the lignocellulosic component of plants by different possible extraction treatments. Both the biomass source and the extraction method affect the structure of the isolated lignin, therefore influencing its further application. Lignin was extracted from beech wood by two different hydrothermal alkaline treatments, which use NaOH and Ba(OH)2 as base and by an acid-catalyzed organosolv process. Moreover, lignin was isolated from bamboo, beech wood and coconut by soda treatment of the biomasses. A comparison of the structural features of such isolated lignins was performed through the use of a wide range of analytical methods. Alkaline lignins resulted in a better candidate as carbon precursor and macromonomers for the synthesis of polymer than organosolv lignin. In fact, alkaline lignins showed higher residual mass after carbonization and higher content of the reactive hydroxy functionalities. In contrast, the lignin source turned out to slightly affect the lignin hydroxyl content.
One of the most common lignin modifications is its deconstruction to obtain aromatic molecules, which can be used as starting materials for the synthesis of fine chemicals. Lignin deconstruction leads to a complex mixture of aromatic molecules. A gas chromatographic analytical method was developed to characterize the mixture of products obtained by lignin deconstruction via heterogeneous catalytic hydrogenolysis. The analytical protocol allowed the quantification of three main groups of molecules by means of calibration curves, internal standard and a preliminary silylation step of the sample. The analytical method was used to study the influence of the hydrogenolysis catalyst, temperature and system (flow and batch reactor) on the yield and selectivity of the aromatic compounds.
Lignin extracted from beech wood by a hydrothermal process using Ba(OH)2 as base, was functionalized by aromatic nitration in order to add nitrogen functionalities. The final goal was the synthesis of a nitrogen doped carbon. Nitrated lignin was reduced to the amino form in order to compare the influence of different nitrogen functionalities on the porosity of the final carbon. The carbons were obtained by ionothermal treatment of the precursors in the presence of the eutectic salt mixture KCl/ZnCl2 Such synthesized carbons showed micro-, macro- and mesoporosity and were tested for their electrocatalytic activity towards the oxygen reduction reaction. Mesoporous carbon derived from nitro lignin displayed the highest electrocatalytic activity.
Lignins isolated from coconut, beech wood and bamboo were used as macromonomers for the synthesis of biobased polyesters. A condensation reaction was performed between lignin and a hyper branched poly(ester-amine), previously obtained by condensation of triethanolamine and adipic acid. The influence of the lignin source and content on the thermochemical and mechanical properties of the final material was investigated. The prepolymer showed adhesive properties towards aluminum and its shear strength was therefore measured. The gluing properties of such synthesized glues turned out to be independent from the lignin source but affected by the amount of lignin in the final material.
This work shows that, although still at a laboratory scale, the valorization of lignin can overcome the critical issues of lignin´s structure variability and complexity.
On the evidential use of English adverbials and their equivalents in Romance languages and Russian
(2017)
The present study investigates the use of equivalents of the English adverbials seemingly and apparently with a specific morphological structure in Romance languages and Russian, i.e. Spanish al parecer, Portuguese ao parecer and ao que parece, French avoir l’air de, Italian all’apparenza and in apparenza as well as Russian по-видимому. The underlying hypothesis is that the function and syntactic behaviour of these adverbial locutions are motivated by their morphological composition. It is to investigate whether the adverbials may be used sentence-initially, parenthetically, as an adverbial with broad or narrow scope or as a component of a modalised predication. The adverbial locutions are treated as means of expression where evidentiality and epistemic modality represent overlapping functional-semantic categories.