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‘Smart’ Janus emulsions
(2021)
Emulsions constitute one of the most prominent and continuously evolving research areas in Colloid Chemistry, which involves the preparation of mixtures or dispersions of immiscible components in a continuous medium. Besides conventional oil-in-water or water-in-oil emulsions, other emulsions of complex droplet morphologies have recently attracted significant research interests. Especially Janus emulsions, in which each droplet is comprised of two distinct sub-regions, have shown versatile potential applications. One of their advantages is the possibility of compartmentalization, which enables to play with two different chemistries in a single droplet. Though microfluidic methods are conventionally used to prepare Janus emulsions, their industrial applications are largely hindered by low throughput and extensive instrumentations. Recently, it has been discovered that simply one-pot moderate/high energy emulsification is also capable of developing Janus morphology, although their preparation and stabilization remain rather substantially challenging. This cumulative doctoral thesis focuses on the preparation and characterization of ‘smart’ Janus emulsions, i.e. Janus emulsions with special stimuli-responsive features. One-step moderate/high energy emulsification of olive and silicone oil in an aqueous medium was carried out. Special consideration was devoted to the interfacial tensions among the components to maintain the criteria of forming characteristic droplet architectures, in addition to avoiding multiple emulsion destabilization phenomena like imminent phase separation or even separated droplet formation. A series of investigations were conducted related to the formation of complexes of charged macromolecules and role of them as stabilizers to achieve stable Janus emulsions for a realistic timeframe (more than 3 months). The correlation between the size of the stabilizer particles and the droplet size of emulsion was established. Furthermore, it was observed that Janus emulsion gels with interesting rheological properties can be fabricated in the presence of suitable polyelectrolyte complexes. Janus emulsions that could be influenced by pH, temperature or magnetic field were successfully produced in presence of characteristic stimuli-responsive stabilizers. Afterwards, the effect of these changes was studied by different characterization techniques. The size and morphology could be tuned easily by changing the pH. The incorporation of iron oxide magnetic nanoparticles (synthesized separately by a co-precipitation method) to one component of the Janus emulsion was carried out so that the movement and orientation of the complex droplets in aqueous media could be controlled by an external magnetic field. Additionally, temperature-triggered instantaneous reversible breakdown of Janus droplets was also accomplished. The responses of the Janus droplets by the stimuli were well-documented and explained. Another goal of the present contribution was to exploit this special morphological feature of emulsions as a template for producing porous materials. This was demonstrated by the preparation of ultralight magnetic responsive aerogels, utilizing Janus emulsion gels. The produced aerogels also showed the capacity to separate toxic dye from water. To the best of our knowledge, this is the first example of investigation towards batch scale production of Janus emulsion with such special stimuli-responsive properties by a simple bulk emulsification method.
Der Charakter Preußens als composite monarchy prägte seine Geschichte, wobei die politischen und territorialen Verwerfungen zu Beginn des 19. Jahrhunderts besondere Herausforderungen zur Integration der 1815 hinzugewonnenen Landesteile mit sich brachten – schließlich liefen sie parallel zu den gesellschaftlichen und ökonomischen Wandlungsprozessen jener ,Sattelzeit‘.
Die Potsdamer Dissertation widmet sich erstmals mit vergleichendem Blick der wirtschaftlichen Integration zweier Gebiete, denen unter den preußischen Neuerwerbungen von 1815 seitens der bisherigen Forschung weniger Aufmerksamkeit geschenkt wurde: das zuvor schwedische Vorpommern sowie diejenigen von Sachsen abgetretenen Territorien, die der dann entstehenden Provinz Brandenburg zugeordnet wurden, einschließlich der Niederlausitz. Quellenbasiert und methodisch fundiert arbeitet die Studie heraus, inwiefern es gelang, diese neuen Landesteile wirtschaftlich in den preußischen Gesamtstaat zu integrieren und so einen einheitlichen Wirtschaftsraum zu konstituieren. In welchem Maße staatliche und nicht-staatliche Akteure aus den Provinzen an dem Integrationsprozess beteiligt waren, ist dabei von besonderem Interesse. Lagen Hemmnisse etwa eher in Strukturen oder eher in dem Verhalten maßgeblicher Personen und Institutionen begründet? Warum stellte sich ein administratives oder legislatives Vorgehen in einem Gebiet als erfolgreich heraus, während es andernorts mehr Widerstände hervorrief? Welche Bedeutung kam außerdem der allgemeinen wirtschaftlichen Verfassung und deren Entwicklung während der beginnenden Industrialisierung für die Integrationsfähigkeit eines Gebietes zu? Durch den Vergleich der Territorien lassen sich die Motive der Beteiligten sowie Bedingungen und Einflussfaktoren für die wirtschaftliche Integration identifizieren.
Das Spannungsfeld zwischen dem Ausbau erneuerbarer Energien einerseits und Akzeptanzproblemen andererseits adressiert der Landesgesetzgeber Mecklenburg-Vorpommerns mit einem Beteiligungsgesetz zur verpflichtenden wirtschaftlichen Teilhabemöglichkeit. Dabei stellt sich die Frage nach der Vereinbarkeit mit geltendem Recht, insbesondere ob der Landesgesetzgeber gesetzgebungsbefugt ist. Darüber hinaus zeigt der Autor den Rahmen für eine Regelung auf und positioniert sich zu möglichen Grundrechtseingriffen durch eine solche Regelung. Die Aktualität der Untersuchung zeigt die gegen das Gesetz anhängige Verfassungsbeschwerde ebenso wie die dynamische Gesetzgebung – so statuiert § 36g Abs. 5 EEG nunmehr eine Länderöffnungsklausel.
Werbeblocker im Internet
(2021)
Werbeblocker berühren zahlreiche, bislang ungeklärte Rechtsfragen. Während Werbeblocker bisher vor allem anhand des Lauterkeitsrechts beurteilt worden sind, zeigt diese Arbeit, dass vielmehr urheberrechtliche Wertungen entscheidend sind. Diese werden mit Blick auf die aktuelle Rechtsprechung des EuGH ausführlich hergeleitet.
Weiterhin wird der Begriff des Mitbewerbers im Lauterkeitsrecht fortentwickelt und mit der Bezugnahme auf die geschäftlichen Entscheidung auf ein neues Fundament gestellt.
Die Arbeit analysiert zudem umfassend die Rechtmäßigkeit der Handlungsalternativen der Webseitenbetreiber und der Reaktionsmöglichkeiten der Werbeblocker aus lauterkeitsrechtlicher und urheberrechtlicher Sicht unter Berücksichtigung der DS GVO.
In modern times of evolving globalization and continuous technological developments, organizations are required to respond to ever-changing demands. Therefore, to be successful in today’s highly uncertain environments, organizations need employees to actively search for opportunities, anticipate challenges, and act ahead. In other words, employee proactivity in the workplace represents a highly valuable resource in nowadays organizations. Empirical studies conducted as part of this thesis advance the research on the outcomes of proactivity from the individual perspective. The main contribution of this thesis pertains to revealing several important individual and contextual conditions under which engaging in proactivity will have negative and positive effects on employees’ well-being and their consequent behaviours, as well as shedding light on the unique psychological mechanisms through which these effects unfold. From a practical standpoint, this research underscores the importance of creating work environments that support employees’ autonomous motivation for proactivity and urge organizations and managers to be mindful about the pressures they place on employees to be proactive at work. Besides, this thesis stimulates research efforts aimed at further extending our knowledge of when and how individual proactive behaviours at work will do more good than harm for those who enact them.
Wandlungsfähige Verwaltungen
(2021)
Vom Gast zum Gastwirt?
(2021)
Die Arbeitsmigration zählt zu den prägenden gesellschaftlichen Wandlungsprozessen der deutschen Nachkriegsgeschichte. 14 Millionen »Gastarbeiter« kamen zwischen 1955 und 1973 in die Bundesrepublik, etwa 3 Millionen von ihnen kehrten nicht in ihre Heimatländer zurück. Vor allem Türkeistämmige blieben nach dem Anwerbestopp häufiger in Deutschland als die Arbeitskräfte aus anderen Ländern. Wie keine andere Stadt steht Berlin bis heute für die Einwanderung aus der Türkei.
Stefan Zeppenfeld untersucht den Wandel der türkischen Arbeitswelten von ihren Anfängen in den 1960er Jahren bis zur Wiedervereinigung. Ausgehend von der »Gastarbeit« im industriellen Großbetrieb spürt er in seiner Studie am Beispiel West-Berlins dem Übergang in andere Branchen nach. Er zeigt, wie der öffentliche Dienst auch für Migrantinnen und Migranten attraktive Aufstiegsmöglichkeiten eröffnete, zeichnet den schwierigen Weg in die gewerbliche Selbstständigkeit nach und legt illegale Beschäftigungsformen als alternative Verdienstmöglichkeit offen.
Damit bettet der Autor die Geschichte der türkischen Arbeitsmigration in die deutsche Zeitgeschichte ein.
Vertragsgestaltung ist ein praktisch sehr relevantes Thema, das wegen der Justizorientierung in der Wissenschaft noch weitgehend stiefmütterlich behandelt wird. In dieser Untersuchung wird, zumindest für die besonders delikate Konstellation bei komplexen Kooperationen des Staats mit Privaten (ÖPP/PPP), Abhilfe geschaffen. Dabei gründet die Analyse auf einer fundierten Typisierung und Charakterisierung der Probleme solcher Projekte. Den theoretischen Rahmen liefert eine effizienzorientierte Studie institutionenökonomischer Ansätze, namentlich der Transaktionskostentheorie und der Prinzipal-Agenten-Theorie, rückversichert über die praxisorientierten Grundregeln der vertraglichen Risikoverteilung. So gelingt es praktische Formulierungsvorschläge für Standardprobleme der Vertragsgestaltung, wie Leistungsbestimmungen, Anpassungsmechanismen, Konfliktbeilegungsregeln, Informationsmechanismen und Kündigungsregeln zu finden. Diese werden auch aus den Erfolgsbedingungen erläutert.
Urteil und Anschauung
(2021)
Wie hier durch textnahe und argumentative Rekonstruktion erstmals gezeigt wird, entwickelt Kant in der Metaphysischen Deduktion in drei Schritten: (i) einen Begriff des Urteils, auf dem die Tafel logischer Funktionen beruht; (ii) einen Begriff der Synthesis der Anschauung, der die Inhalte der Kategorien erklärt; und (iii) einen Begriff des Verstandes, demzufolge die Kategorien a priori zu demselben Vermögen gehören, durch das wir auch urteilen.
Die vorliegende Untersuchung ist eine argumentative Rekonstruktion von Kants Text. Der rekonstruierte Text ist der „Leitfaden der Entdeckung aller reinen Verstandesbegriffe" auf A 64 bis 83 / B 89 bis 113 der Kritik der reinen Vernunft in ihren beiden Auflagen von 1781 (A) und 1787 (B). Zudem werden andere, für ein Verständnis der Überlegungen in diesem Kapitel erforderliche oder zumindest erhellende Textstellen aus der Kritik herangezogen; aus Schriften, die Kant nach der Kritik geschrieben hat; sowie schließlich aus Kants Nachlass-Notizen und aus Nachschriften zu seinen Vorlesungen jeweils seit der Entstehungszeit der Kritik. Von entscheidender Bedeutung sind dabei vor allem vier weitere Passagen der Kritik selbst: i) die rückblickende Beschreibung der Aufgabe der Metaphysischen Deduktion auf B 159, ii) die rückblickende Beschreibung des Vorgehens im „Leitfaden" auf A 299/B 355 f., iii) der Abschnitt „Von den Gründen a priori zur Möglichkeit der Erfahrung" auf A 95 bis 110 der Transzendentalen Deduktion der Kategorien in der ersten Auflage und schließlich iv) die §§ 15 bis 21 auf B 128 bis 148 der Transzendentalen Deduktion der Kategorien in der zweiten Auflage der Kritik.
Vor dem Hintergrund einer umfassenden und detaillierten Analyse des „Leitfadens", bei Hinzuziehung verwandter Stellen aus dem umgrenzten Textbestand und nicht zuletzt bei Berücksichtigung des Verhältnisses des „Leitfadens" zu den genannten vier Passagen der Kritik legt sich eine Interpretation der Metaphysischen Deduktion nahe, die sich nur schwer bestreiten lässt, sobald diese Texte einmal gemeinsam betrachtet und auf eine bestimmte Weise zueinander ins Verhältnis gesetzt werden. Dabei kann eine durchgehend wohlwollende, argumentative Rekonstruktion dazu beitragen, auch die philosophische Überzeugungskraft der Position Kants deutlich zu machen.
In der vorliegenden Arbeit wird die Geschichte des militärischen Transfusionswesens in Deutschland, ausgehend vom Deutsch-Französischen Krieg, über den Ersten und Zweiten Weltkrieg, bis hin zu der Organisation des Blutspendewesens sowie der Herstellung von Blut- und Blutbestandteilkonserven in der NVA, aber auch der Bundeswehr analysiert, Gemeinsamkeiten und Unterschiede der einzelnen Epochen und Armeen aufgezeigt sowie rückblickend ethische Problemfelder identifiziert und aufgearbeitet. Zusätzlich werden die den jeweiligen Zeiträumen zugeordneten technischen Apparaturen und Verfahren sowie zeitgenössische Forschungsprojekte skizziert.
The trace elements zinc and manganese are essential for human health, especially due to their enzymatic and protein stabilizing functions. If these elements are ingested in amounts exceeding the requirements, regulatory processes for maintaining their physiological concentrations (homeostasis) can be disturbed. Those homeostatic dysregulations can cause severe health effects including the emergence of neurodegenerative disorders such as Parkinson’s disease (PD). The concentrations of essential trace elements also change during the aging process. However, the relations of cause and consequence between increased manganese and zinc uptake and its influence on the aging process and the emergence of the aging-associated PD are still rarely understood. This doctoral thesis therefore aimed to investigate the influence of a nutritive zinc and/or manganese oversupply on the metal homeostasis during the aging process. For that, the model organism Caenorhabditis elegans (C. elegans) was applied. This nematode suits well as an aging and PD model due to properties such as its short life cycle and its completely sequenced, genetically amenable genome. Different protocols for the propagation of zinc- and/or manganese-supplemented young, middle-aged and aged C. elegans were established. Therefore, wildtypes, as well as genetically modified worm strains modeling inheritable forms of parkinsonism were applied. To identify homeostatic and neurological alterations, the nematodes were investigated with different methods including the analysis of total metal contents via inductively-coupled plasma tandem mass spectrometry, a specific probe-based method for quantifying labile zinc, survival assays, gene expression analysis as well as fluorescence microscopy for the identification and quantification of dopaminergic neurodegeneration.. During aging, the levels of iron, as well as zinc and manganese increased.. Furthermore, the simultaneous oversupply with zinc and manganese increased the total zinc and manganese contents to a higher extend than the single metal supplementation. In this relation the C. elegans metallothionein 1 (MTL-1) was identified as an important regulator of metal homeostasis. The total zinc content and the concentration of labile zinc were age-dependently, but differently regulated. This elucidates the importance of distinguishing these parameters as two independent biomarkers for the zinc status. Not the metal oversupply, but aging increased the levels of dopaminergic neurodegeneration. Additionally, nearly all these results yielded differences in the aging-dependent regulation of trace element homeostasis between wildtypes and PD models. This confirms that an increased zinc and manganese intake can influence the aging process as well as parkinsonism by altering homeostasis although the underlying mechanisms need to be clarified in further studies.
Water-deficits can cause lethal damage to organisms, which is rooted in cellular dehydration. Many plant species, but also other organisms have developed mechanisms to tolerate such stresses, such as the expression of LEA proteins. Many studies report on physiological protective functions of LEA proteins but lack information about their precise mechanisms on a molecular level. Most LEA proteins are intrinsically disordered in dilute solution but may adopt a distinct secondary structure upon changes in solvent conditions. Understanding the molecular mechanism of how LEA proteins contribute to the counteraction of cellular damage during water-deficits may in the long-term pave the way for breeding crops that are resistant to the effects of global warming. The objective of the work at hand is to improve the biophysical understanding of the sequencestructure-function relationship of LEA proteins as membrane stabilizers, based on the LEA_4 family of the model plant A. thaliana. This is pursued by using a combination of spectroscopic and scattering techniques, supported by bioinformatics and computational analyses. Eight out of the 18 LEA_4 proteins are experimentally assessed revealing that a coil-helix transition in response to water-deficit is a common feature, as predicted for the entire family. In addition, they all stabilize simple membrane models during a freeze/ thaw cycle. Three-dimensional structure prediction of representative members suggests that their completely folded states are represented by a sequential arrangement of alpha-helical segments connected by unstructured linkers, which is experimentally verified for the LEA_4 protein COR15A. The unstructured linker region of COR15A represents a conserved motif among its closest homologs and is, therefore, of particular interest. Facilitating a set of seven designed and investigated COR15A mutants uncovers a complex interplay of transient interactions between the amphipathic alpha-helical segments, mediated by the linker, which fine-tunes folding transitions and structural ensembles upon reduced water-availability. Finally, alpha-helicity is also induced in COR15A upon temperature decrease, which is enhanced in the presence of osmolytes. In addition, high solution osmolarity induced secondary structure is followed by oligomerization of COR15A. Interestingly, the functionality of COR15A, in terms of liposome stabilization, strongly correlates with its alpha-helix ratio in the folded state. The present work significantly improves the understanding of the sequence-structure-function relationship for LEA_4 proteins and offers novel findings on folding mechanisms and oligomerization of COR15A.
Patterning along the apical-basal (A-B) axis is a crucial step during the early stages of plant embryogenesis and leads to the establishment of two poles of which each will develop their own stem cell niches. The activity of these meristems is responsible for post-embryonic growth, with the shoot apical meristem (SAM) generating the above-ground organs and the root apical meristem (RAM) producing the subterranean structures of the plant. While several transcriptional regulators governing A-B patterning have been identified, precisely how their regulatory function is orchestrated remains elusive. This study focuses on transcriptional co-regulators LEUNIG (LUG) and closely related LEUNIG_HOMOLOG (LUH) and their role in the formation of A-B patterning during embryogenesis as well as their post-embryonic maintenance. A link between the LUG regulatory complex and SAM formation and maintenance comes from the observation that lug mutants heterozygous for the luh allele (lug luh+/-) often have enlarged SAMs resulting from misregulated cell divisions. A more severe phenotype is observed in lug luh double mutants which are embryonically lethal. In this study, a detailed characterisation of lug luh embryo phenotype reveals that these mutants display aberrant cell divisions along the A-B axis, which correlates with defects in auxin distribution, complete loss of apical identity, and altered expression of transcription factors determining basal fate. Like other co-regulators, LUG and LUH lack intrinsic DNA-binding domains and instead must interact with DNA-binding cofactors to ensure recruitment to regulatory elements of target genes. This either involves direct contact between the co-regulators and transcription factors (TFs) or the formation of higher-order complexes with adaptor proteins such as SEUSS (SEU) or related SEUSS-LIKEs (SLKs), which facilitate binding to specific TFs. Results presented in this study provide insight into the molecular framework for the LUG regulatory complex activity during embryogenesis. Both yeast and in planta assays showed that LUG/LUH and SEU/SLKs physically associate with a variety of WUSCHEL-RELATED HOMEOBOX (WOX) TFs including members of the WOX2-module. Furthermore, genetic interactions between members of the WOX2-module and the LUG regulatory complex, support their mutual action during embryogenesis. Based on the reduced activity of HOMEODOMAIN LEUCINE-ZIPPER CLASS III (HD-ZIPIII) promoters in lug luh embryos, a model is proposed in which the LUG regulatory complex functions together with WOX2-module to promote apical identity and subsequent SAM initiation through regulation of the HD-ZIPIIIs. The activity of the LUG complex in promoting basal embryo identity through positive regulation of microRNA165/166 suggests that this complex also has functions that are independent of the WOX2-module. Preliminary work reported in this study further uncovered the role of the LUG regulatory complex in post-embryonic development. While the fasciated inflorescence meristems of lug luh+/- plants displayed defects in auxin transport and altered activity of stem cell markers, embryonically rescued lug luh mutants formed flat and differentiated SAMs. In addition, rescued lug luh mutants exhibited severely disorganised RAM and defects in quiescent center (QC) specification, supporting the involvement of the LUG complex in post-embryonic RAM maintenance.
The development of type 2 diabetes (T2D) is driven by genetic as well as life style factors. However, even genetically identical female NZO mice on a high-fat diet show a broad variation in T2D onset. The main objective of this study was to elucidate and investigate early epigenetic determinants of type 2 diabetes. Prior to other experiments, early fat content of the liver (<55.2 HU) in combination with blood glucose concentrations (>8.8 mM) were evaluated as best predictors of diabetes in NZO females. Then, DNA methylome and transcriptome were profiled to identify molecular pathophysiological changes in the liver before diabetes onset. The major finding of this thesis is that alterations in the hepatic DNA methylome precede diabetes onset. Of particular interest were 702 differentially methylated regions (DMRs), of which 506 DMRs had genic localization. These inter-individual DMRs were enriched by fivefold in the KEGG pathway type 2 diabetes mellitus, independent of the level of gene expression, demonstrating an epigenetic predisposition toward diabetes. Interestingly, among the list of hepatic DMRs, eleven DMRs were associated with known imprinted genes in the mouse genome. Thereby, six DMRs (Nap1l5, Mest, Plagl1, Gnas, Grb10 and Slc38a4) localized to imprinting control regions, including five iDMRs that exhibited hypermethylation in livers of diabetes-prone mice. This suggests that gain of DNA methylation in multiple loci of the paternal alleles has unfavourable metabolic consequences for the offspring. Further, the comparative liver transcriptome analysis demonstrated differences in expression levels of 1492 genes related to metabolically relevant pathways, such as citrate cycle and fatty acid metabolism. The integration of hepatic transcriptome and DNA methylome indicated that 449 differentially expressed genes were potentially regulated by DNA methylation, including genes implicated in insulin signaling. In addition, liver transcriptomic profiling of diabetes-resistant and diabetes-prone mice revealed a potential transcriptional dysregulation of 17 hepatokines, in particular Hamp. The hepatic expression of Hamp was decreased by 52% in diabetes-prone mice, on account of an increase in DNA methylation of promoter CpG-118. Hence, HAMP protein levels were lower in mice prone to develop diabetes, which correlated to higher liver triglyceride levels.. In sum, the identified DNA methylation changes appear to collectively favor the initiation and progression of diabetes in female NZO mice. In near future, epigenetic biomarkers are likely to contribute to improved diagnosis for T2D.