35 research outputs found

    Practices of emancipation : an analysis of security, dialogue and change in post-war Vukovar

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    The thesis analyses the Croatian city of Vukovar as a way of animating theoretical debates about the relationship between security, emancipation and practice. It claims that emancipation must be understood through experiences of security and insecurity as they are lived. Located in security studies, it begins with a critical reading of the Welsh School. Ken Booth's original move to associate security with emancipation opened up new possibilities for reimagining the field and for practicing security, but subsequent developments orientated the security as emancipation move towards closure. A genuinely open way of exploring this move is the context of Andrew Linklater's adaptation of Habermasian discourse ethics. In this way an engagement between Booth and Linklater is opened which runs throughout the thesis. The second part introduces Vukovar. It details the violence of late-1991 seen in the city, and outlines how the emergence of Croatian democracy represents a form of settlement. Yet patterns of memorialisation and reconstruction in Vukovar entrench a pro-Croat narrative of settlement at the expense of non-Croats who are unjustly excluded. Furthermore, interviews with leaders of local civil society, religious and political groups suggest that difference and contestation, rather than settlement, characterise the post-war period in Vukovar. The third part presents an analysis of the emancipatory practices which take place within the local context of contestation. Interviews with NGOs in Vukovar support Booth's emphasis on civil society groups as agents of emancipation. Subsequent interviews challenge his view in important ways as the human limits of emancipatory practices are revealed. However, even when such limitations are taken into account, certain civil society practices show how Booth and Linklater's respective understandings of emancipatory practice are played out in what are termed microdialogic communities. These alternative dialogues open new spaces and allow dominant understandings of the war to be challenged

    The vesicle transfer ("trans secretion") of membrane components to bovine epididymal sperm

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    Bei der Passage durch den männlichen Reproduktionstrakt interagieren Spermatozoen mit Faktoren, die u.a. vom Nebenhoden sezerniert werden. Die daraus resultierende Modifikation der Spermatozoen ist essentiell für die Ausreifung zu voll funktionsfähigen Keimzellen. Bei der Ausdifferenzierung im Nebenhoden spielen vermutlich u. a. auch die Epididymosomen (apokrin sekretierte Nebenhodenvesikel) eine wichtige Rolle. In vorausgehenden Untersuchungen unserer Arbeitsgruppe konnte gezeigt werden, dass sich die Plasmamembran-Ca2+-ATPase Isoform 4 (PMCA4) Spleißvarianten-Ausstattung in der Membran von Bullenspermien von PMCA4b in Caputspermien zu PMCA4a in Caudaspermien ändert. Zudem nahm auch die Ca2+-ATPase Aktivität der Spermien während der Passage durch den Nebenhoden signifikant zu. Die Möglichkeit eines Transfers der PMCA4a von Epididymosomen auf Spermien wurde postuliert (Sanchez-Luengo et al. 2004,Brandenburger et al. 2011). Ziel der vorliegenden Arbeit war es, die fusogene Eigenschaft boviner Epididymosomen näher zu untersuchen. Dafür wurden Nebenhodenvesikel aus den verschiedenen Nebenhodenabschnitten isoliert und sowohl morphologisch, als auch biochemisch charakterisiert. Weiterhin wurde der vesikuläre Transfer von Membrankomponenten (Lipide, Proteine) und speziell der potentielle Transfer der PMCA auf bovine Nebenhodenspermien untersucht. Elektronenmikroskopische ntersuchungen zeigten, dass Cauda Epididymosomen größer sind als Caput Epididymosomen. Lipidanalysen von Caput- und Cauda Epididymosomen belegten eine Zunahme des Cholesterin/Phospholipid-Verhältnisses bei einer Abnahme der Cholesterol- und der Phospholipidkonzentration. Hauptanteilig konnten die Phospholipide Phosphatidyethanolamin (PE), Phosphatidylcholin (PC) und Sphingomyelin(SM) nachgewiesen werden, wobei sich der Gehalt in Caput- und Cauda Epididymosomen nicht signifikant veränderte. Bei der Proteinanalyse spezialisierte sich die Autorin auf die PMCA. Mittels Westernblot-Analysen konnte gezeigt werden, dass in Cauda Vesikeln mehr PMCA4a nachzuweisen war als in Caput Vesikeln. Auch die Ca2+-ATPase Aktivität stieg von Caput- zu Cauda Epididymosomen signifikant an. Um in in vitro Experimenten die fusogene Eigenschaft der Epididymosomen mit Spermien zu untersuchen, wurden bovine Epididymosomen mit dem Fluoreszenzfarbstoff Octadecylrhodamin B (R18) markiert. Für Caputspermien konnte eine höhere Fusionsrate als für Caudaspermien nachgewiesen werden. Der für die Fusion optimale pH lag dabei im sauren Bereich (pH 5 - 6). Lipidanalysen von Nebenhodenspermien belegten eine Abnahme des Cholesterin/Phospholipid-Verhältnisses von Caput- zu Caudaspermien. Dies konnte auch nach in vitro Fusion von Caputspermien mit Epididymosomen erzielt werden. Daher wird postuliert, dass diese Veränderungen ein Ergebnis aus der Interaktion der Spermien mit den Epididymosomen sind. In vivo konnte in Spermien eine Abnahme von PE, PC und SM im Verlauf des Nebenhodentraktes dokumentiert werden, die jedoch in vitro nicht nachgeahmt werden konnte. Nach Markierung der Epididymosomen mit Biotin konnte eine Übertragung Biotin-markierter Proteine von Epididymosomen auf die Nebenhodenspermienmembran mittels in vitro Fusion gezeigt werden. Die Ca2+-ATPase-Aktivität nahm zwar signifikant nach in vitro Fusion von Epididymosomen mit Nebenhodenspermien zu, ob aber auch die PMCA4a übertragen wird, konnte mittels Immunhistologie nicht abschließend geklärt werden, da der Antikörper gegen die Spleißvariante PMCA4a auf Spermienausstrichen unzureichend färbte. Lediglich mit dem Antikörper gegen PMCA4 konnte eine leichte Fluoreszenzzunahme im Mittelstück dokumentiert werden, die auf eine Übertragung hindeuten könnte. Weiterhin konnte in vorausgehenden Untersuchungen unserer Arbeitsgruppe gezeigt werden, dass die Ca2+-ATPase Aktivität in Nebenhodenspermien organspezifisch (z.B. keine signifikante Stimulation in Herz und Niere) durch das Bläschendrüsenprotein PDC-109 signifikant stimuliert werden kann (Sanchez-Luengo et al. 2004). Diese Stimulation konnte in der vorliegenden Arbeit auch für Epididymosomen und Spermien nach in vitro Fusion dokumentiert werden. Es ist bekannt, dass PDC-109 an Phospholipide bindet und auch die Aktivität der PMCA durch Phospholipide beeinflusst werden kann. Weitere Untersuchungen müssen zeigen, ob es einen Zusammenhang zwischen der Lipidveränderung und der erhöhten Ca2+-ATPase Aktivität in Spermien nach der Fusion gibt. Zusammenfassend führt die Transsekretion (Zell-zu-Zelltransfer) zwischen Epididymosomen und Spermien zur Übertragung von Lipiden und Proteinen mit Einfluss auf die Ca2+-ATPase-Aktivität.During the passage through the male reproduction tract spermatozoa interact with factors, which amongst others are released from the epididymis. The outcome of the spermatozoa modification is essential for the maturation to full functional germ cells. During the differentiation in the epididymis the epididymosomes (apocrin secreted epididymal vesicles) play a crucial role. Previous work of our group demonstrated a switch of the plasma membrane Ca2+-ATPase isoform 4 (PMCA4) splice variants from PMCA4b in bovine caput spermatozoa membrane to PMCA4a in bovine cauda spermatozoa membrane. In addition the Ca2+-ATPase activity of spermatozoa increased significantly during the transit through the epididymidis. The possibility of a transfer of PMCA4a from epididymosomes to spermatozoa was postulated (Sanchez-Luengo et al. 2004, Brandenburger et al. 2011). The aim of the present study was analyze the fusogen properties of epididymosomes closely. Therefore, epididymal vesicles were isolated from different epididymal regions. After this, epididymosomes were characterized morphologically as well as biochemically. Furthermore, the vesicle transfer of membrane components (lipids, proteins) was analyzed, especially the potential transfer of PMCA to bovine epididymal spermatozoa. Electron microscopical analyses showed, that cauda epididymosomes are greater than caput epididymosomes. Lipid analyses of caput and cauda epididymosomes proved an increase of the cholesterol/phospholipid rate with a decrease of cholesterol and phospholipid concentration. The phospholipids Phosphatidylethanolamine (PE), Phosphatidylcholine (PC) and Sphingomyeline(SM) were predominantly detected, whereby the concentration in caput and cauda epididymosomes was not significantly modified. For protein analyses, the author focused on PMCA. By means of Westernblot analyses, it could be shown, that cauda vesicles exhibit more PMCA4a than caput vesicles. Also the Ca2+-ATPase activity increased significantly from caput to cauda epididymosomes. To determine in in vitro experiments, the fusogen properties of bovine epididymosomes with spermatozoa, bovine epididymosomes were labeled with the fluorescent dye Octadecylrhodamin B (R18). Caput spermatozoa showed a higher fusion rate than cauda spermatozoa. The optimal pH value for the fusion was in the acid area (pH 5 - 6). Lipid analyses of epididymal spermatozoa proved a decrease of the cholesterol/phospholipid rate from caput to cauda spermatozoa. This could also be achieved after in vitro fusion of caput spermatozoa with epididymosomes. Therefore, it is postulated, that this modification is a result of the interaction from spermatozoa with epididymosomes. In vivo it was documented that the concentration of PE, PC and SM decreased in spermatozoa during passing through the epididymis, whereby in vitro no alterations were etermined. After labeling the epididymosomes with Biotin, a transfer of biotin-labeled proteins of epididymosomes on epididymal spermatozoa membrane could be shown by in vitro fusion. In fact the Ca2+-ATPase activity increased significantly after in vitro fusion of epididymosomes with spermatozoa. Nevertheless, transfer of PMCA4a could not be clarified definitively by immuncytology, because the antibody against PMCA4a reacted deficient on spermatozoa smear. Using the antibody against PMCA4 a slight increase of fluorescence was shown in the middle piece of spermatozoa tail. Furthermore, previous work of our group showed that the Ca2+-ATPase activity of epididymal spermatozoa is stimulated organ-specific by the seminal vesicle major protein PDC-109 respectively (no significant stimulation in heart and kidney) (Sanchez-Luengo et al. 2004). In this study, this stimulation could also be documented for epididymosomes and spermatozoa after in vitro fusion. It is well-known that PDC-109 binds on phospholipids and that the PMCA activity can be affected by phospholipids. Further analyses have to display potential correlation between lipid modification and the increase of Ca2+-ATPase activity in spermatozoa after in vitro fusion. In summary, the trans secretion (cell-to-cell transfer) between epididymosomes and spermatozoa resulted in a disposition of lipids and proteins with influencing Ca2+-ATPase-activity

    Kooperativitätseffekte in multivalenten Kronenether/Ammonium-Komplexen

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    Acknowledgements Abstract Kurzzusammenfassung 1 Introduction 2 Theoretical background 2.1 Host–guest complexes 2.1.1 The crown ether/ammonium binding motif 2.1.2 Solvent effects 2.1.3 Counterion effects 2.2 Multivalency 2.3 Cooperative effects in multivalent systems 2.3.1 Allosteric cooperativity 2.3.2 Chelate cooperativity 2.3.3 Interannular cooperativity 2.3.4 The double mutant cycle analysis 2.3.5 Statistical factors 2.4 Isothermal titration calorimetry 3 Published work 3.1 Theoretical and experimental investigation of crown/ammonium complexes in solution 3.1.1 Project summary 3.1.2 Author contributions 3.2 Allosteric and chelate cooperativity in divalent crown ether/ammonium complexes with strong binding enhancement 3.2.1 Project summary 3.2.2 Author contributions 3.3 Thermodynamic analysis of allosteric and chelate cooperativity in di- and trivalent ammonium/crown-ether pseudorotaxanes 3.3.1 Project summary 3.3.2 Author contributions 3.4 The delicate balance of preorganisation and adaptability in multiply bonded host–guest complexes 3.4.1 Project summary 3.4.2 Author contributions 3.5 Gating the photochromism of an azobenzene by strong host–guest interactions in a divalent pseudo[2]rotaxane 3.5.1 Project summary 3.5.2 Author contributions 3.6 Discrete multiporphyrin pseudorotaxane assemblies from di- and tetravalent porphyrin building blocks 3.6.1 Project summary 3.6.2 Author contributions 4 Conclusion Bibliography Appendix A.1 J. Comput. Chem. 2016, 37 (1), 18–24 A.2 Chem.—Eur. J. 2016, 22 (43), 15475–15484 A.3 Org. Lett. 2015, 17 (20), 5076–5079 A.4 Chem.—Eur. J. 2017, 23 (12), 2877–2883 A.5 Chem. Commun. 2015, 51 (48), 9777–9780 A.6 Beilstein J. Org. Chem. 2015, 11 (4), 748–762Multivalency is a molecular organisation principle to generate strong and reversible intermolecular interactions. Generally speaking, there are two opposing design principles for constructing synthetic multivalent systems: the first exploits rigid and preorganised building blocks to reduce the entropic penalty of the binding event. Although widely used in supramolecular chemistry, such rigid complexes are sensitive to small geometric mismatches. The second concept—often found in nature—avoids this sensitivity by implementing adaptable, more flexible building blocks. At present, it remains unclear as to which approach leads to more stable multivalent interactions. Decoupling the multivalent association amplification into its component parts—allosteric and chelate cooperativity—can elucidate the operating principles behind the multivalent interaction, the impacts of structural flexibility, and promote a better understanding of the effect. In turn, a deeper understanding of these effects can inform a general “toolkit” for tuning multivalent interactions towards specific applications. To address both questions regarding the general mechanisms governing the multivalency effect and the adaptability–preorganisation dichotomy, we investigated the cooperative effects in crown ether/ammonium assemblies with varying numbers of binding sites and different spacer lengths and flexibilities. The thermodynamic analysis by isothermal titration calorimetry was complemented by density functional theory calculations and molecular dynamics simulations. The combined approach revealed a number of effects operating in the systems. The ion-pairing between ammonium guests and their respective counterions strongly affects allosteric cooperativity in the guests. This is counterbalanced by the polarity of the chosen solvent. In the hosts, polarisable π-systems cause negative allosteric cooperativities. As expected, small geometric mismatches in rigid systems cause a significant drop in chelate cooperativity. The flexible guests are less affected by geometric mismatches and, surprisingly, generally exceed the more rigid structures in chelate cooperativity. The ability of flexible spacers to correct for small geometric mismatches between host and guest overcomes the entropic penalty incurred through conformational restriction during binding. Moreover, favourable secondary spacer–spacer interactions surpass any entropic penalty. A delicate balance between preorganisation and adaptability is at play when multiply bonded structures are concerned. From these findings, we derived our general toolkit: adaptable, complementary systems are preferable over rigid preorganised systems with respect to strong, reliably working multivalent interactions. Using our newly developed toolkit, we demonstrate the successful tuning of a photoswitch. Furthermore, we applied our design principle to program the self assembly of di- and tetravalent porphyrin-based crown ether and ammonium building blocks into discrete assemblies. The rigidity of the porphyrin scaffold is necessary for complementarity and directionality of the interactions and rotational flexibility between porphyrin scaffold and binding sites for correction of possible mismatches. These and similar structures are promising building blocks for the construction of more complex assemblies inheriting function in the future.Durch Multivalenz können auf molekularer Ebene starke und dennoch reversible Wechselwirkungen erzeugt werden. Dabei gibt es zwei gegensätzliche Ansätze, um dieses molekulare Organisationsprinzip zu optimieren: Im ersten Ansatz wird versucht, den Entropieverlust zu minimieren, der aus der Einschränkung der konformellen Freiheitsgrade im gebundenen Zustand herrührt. Dafür werden starre, vororganisierte Grundbausteine verwendet, welche bereits im ungebundenen Zustand wenig konformelle Freiheitsgrade besitzen. Sie haben jedoch den Nachteil, dass bereits kleine geometrische Unstimmigkeiten zwischen den Bindungspartnern ungünstige Spannungen im Komplex hervorrufen. Der zweite Ansatz versucht, diese Spannungen durch flexiblere, anpassungsfähige Grundbausteine zu umgehen. Viele Systeme in der Natur verwenden dieses zweite Konzept. In der supramolekularen Chemie ist jedoch das erste Konzept verbreitet. Die Untersuchung der kooperativen Effekte (allosterische und Chelatkooperativität) in einem multivalenten System kann Aufschluss darüber geben, welcher der beiden Ansätze zuverlässiger ist. Außerdem können Hinweise auf die Mechanismen, die der multivalenten Bindungsverstärkung zugrunde liegen, gewonnen werden. Um beide Fragestellungen anzugehen, wurden die kooperativen Effekte in Kronenether/ Ammonium-Komplexen abhängig von Flexibilität und Länge des Gastbausteins untersucht. Die thermodynamische Untersuchung mit isothermer Titrationskalorimetrie wurde durch Dichtefunktionaltheorie- und Moleküldynamikrechnungen ergänzt. Diese Untersuchungen deckten ein komplexes Zusammenspiel von Lösungsmittel- und kooperativen Effekten auf. Die allosterische Kooperativität in den Gastmolekülen wird hauptsächlich von der lösungsmittelabhängigen Ionenpaarbildung zu ihren Gegenionen hervorgerufen. In den Wirtmolekülen wird negative allosterische Kooperativität durch die Polarisierbarkeit ihrer π-Systeme verursacht. Die Chelatkooperativität in Komplexen mit flexiblen Gaststrukturen ist im Gegensatz zu den starren weitgehend unabhängig von strukturellen Unstimmigkeiten zwischen Wirt- und Gastmolekülen. Überraschenderweise haben Komplexe mit flexiblen Gaststrukturen generell höhere Chelatkooperativitäten als die mit starren. Die Anpassungsfähigkeit der flexiblen Strukturen scheint die Chelatkooperativität positiv zu beeinflussen. Dabei werden die durch die multivalente Bindung hervorgerufenen Entropieverluste kompensiert. Hinzu kommen enthalpisch günstige sekundäre Wechselwirkungen der Verknüpfungsstrukturen (spacer) zwischen den einzelnen Bindungsstellen. In multivalenten Systemen herrscht ein fragiles Gleichgewicht zwischen Anpassungsfähigkeit und Vororganisation. Für die Entwicklung eines verlässlich funktionierenden multivalenten Systems sollten komplementäre, anpassungsfähige Strukturen bevorzugt eingesetzt werden. Mithilfe dieser Erkenntnisse konnten wir eine supramolekulare, multivalente Wechselwirkung nutzen, um die Funktion eines Photoschalters zu steuern. Die erworbenen Kenntnisse zum Anpassungsfähigkeits/Vororganisations-Gleichgewicht ermöglichten es uns, die Selbstanordnung (self-assembly) von di- und tetravalenten Kronenether und Ammoniumbausteinen erfolgreich zu programmieren. Diese Strukturen sind vielversprechende Vorläufer für eine künftige Anwendung im Aufbau komplexerer Strukturen mit funktionalen Eigenschaften

    Caesarean sections on request: Perceptions and positions (1996-2008)

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    This thesis examines perceptions of caesarean sections on request from the mid-1990s to 2008, and in particular the meaning of the term and how this mode of delivery has affected doctors’ practice, as well as the opinions of expectant mothers. Within the field of obstetrics, caesareans on request represent a highly relevant issue, not only because a quarter of all births are currently by caesarean delivery. However, despite its relevance, this topic has not yet been the subject of substantial academic research. Caesareans on maternal request refer to caesareans with no clinical indications and thus no obvious medical justification – this fact in particular has stirred the medical world as well as evoking disputes among pregnant women. By exploring the views of medical professionals and mothers-to-be, this thesis uses an interdisciplinary approach, combining aspects of medical history and the social sciences. Furthermore, it goes beyond the clinical perspective by researching popular scientific publications, such as advice books and even debates on online forums. The phenomenon of caesareans on request suggests a change in indications, as well as a shift from caesarean delivery as an emergency intervention to a viable option. It involves an interaction between patient autonomy, risk assessment and prevention; furthermore, obstetric behaviour and changes in medical attitudes have played their part in providing the grounds for making maternal choice possible

    Crafting the "Common Will." The IGC 1996 from an Austrian Perspective. IHS Political Science Series No. 52, December 1997

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    The paper analyses the negotiations that took place in the framework of the Intergovernmental Conference (IGC) 1996/97 leading to the modification and amendment of the founding treaties of the European communities. Taking the Austrian case as an example the interaction between the various actors at the national and the international level is reconstructed. The author criticises the “intergovernmental approach” to the analysis of decision making mechanisms in the EU showing that the negotiations did not follow the logic of state power and multilateral bargaining but a “logic of mutual adaptation of expectations and positions”. The IGC 1996/97 exemplifies the ongoing institutionalisation of peculiar decision making procedures and the proliferation of working methods that were developed in the various arenas of European negotiations. A key element of these methods is the importance of mediating roles like the role played by the Council presidency during the IGC. It is argued that the Amsterdam Treaty represents some sort of a “common will” rather than a diplomatic bargain between sovereign states. This is due to the particular setting of the IGC 1996/97 and organisational arrangements that undermine the boundaries between the intergovernmental and the supranational, the national and the international arena, between international and domestic negotiations, and between the national and the European interest

    Quality of Life and Health Metrics in Young Children at Genetic Risk for Speech and Language Disorder and their Parents: Broad and longitudinal effects of a proactive intervention, the Babble Boot Camp

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    abstract: The objective of this study was to examine the quality of life health metrics of parents whose children were diagnosed with Classic Galactosemia and underwent a proactive treatment program. The data analyzed in this study came from the Babble Boot Camp©, which included one control family and nine treatment families. The Babble Boot Camp© is an innovative intervention program that is implemented via parent training. Child progress and parent quality of life are closely monitored in regular intervals. The purpose of this study was to evaluate if the intervention was successful in terms of child language growth, how the child’s progress affected the parent’s quality of life, and if there were differences in the psychological and physical health of the mothers and fathers. We utilized a variety of questionnaires, specifically the Ages and Stages Questionnaires- 3 (ASQ3) (Squires & Bricker, 2009), Pediatric Quality of Life (PedsQL) Questionnaire (Varni, 1998), Parental Stress Index (PSI-4) (Abidin 2012) and the MacArthur CDI Questionnaire (MBCDI2) (Fenson et al., 2007). The three main findings of this study are: the BBC© treatment protocol showed beneficial gain to the children, the development of the child did affect the parent’s quality of life, and the mother’s physical health was significantly worse than the father’s in terms of health metrics. The significance of this study is to identify preliminary trends in quality of life data of the parents. Clinical implications for the future include investigation of various possible factors driving the improvement of the parent’s quality of life

    Introspective data and corpus data : combination instead of confrontation in the study of German metaphorical idioms of life

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    This paper examines the applicability of the combination of data types in a study of German idioms of life with the tools of cognitive metaphor theory. The data sources for conceptual metaphors were mainly metaphors found in the relevant literature. These metaphors are of introspective nature to a great extent. The primary data sources for metaphorical expressions were dictionaries that represent introspective data, too. These data have been complemented by corpus data. The paper discusses the problems of introspective and corpus data raised by the study of German idioms of life. Two case studies demonstrate the advantages of the combination of data and methods

    Etnicidade e trabalho alemão :: outros usos e outros produtos do labor humano /

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    Dissertação (Mestrado) - Universidade Federal de Santa Catarina, Centro de Filosofia e Ciências Humanas
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