The study aims to investigate the effects of married women&rsquo / s attachment security, caregiving styles, how they initiated marriage (i.e., love vs. arranged) and whether they have egalitarian or traditional marriage on their marital satisfaction and attachment figure transference to their husband. It is expected that attachment to spouse would be stronger and attachment functions would be transferred earlier in love marriages than arranged marriages. Moreover, caregiving styles, attachment security, and egalitarian structure of marriage are expected to predict transference of attachment functions to husbands and marital satisfaction. Married women (N = 204) filled out a questionnaire package including the measures of division of labor in house chores, significant people in their life, attachment anxiety and avoidance, caregiving styles, and marital satisfaction. A series of ANCOVA controlling for the duration of marriage was conducted to compare the participants with arranged and love marriages. Separate hierarchical regression analyses were conducted to predict attachment strength and satisfaction separately for love and arranged marriages. Results revealed no significant difference between arranged and love marriages on the strength and timing of attachment figure transference to spouse. In both types of marriage, sensitive and responsive caregiving styles and low attachment avoidance were associated with stronger attachment to spouse. Although those with egalitarian relationships reported higher levels of marital satisfaction in both love and arranged marriages, women with both egalitarian and love marriages reported the highest levels of marital satisfaction than those with traditional and love marriage. The findings were discussed considering cultural context and previous work.

The upsurge of religious movements and independent churches in the Global South is bringing a new twist to world economic development not anticipated by many theologians and social scientists. With a syncretic soteriology geared toward the liberation of the whole person, religious movements and independent churches of the south are preaching to their adherents, mostly the poor and the marginalized, a message of faith in an omnipotent and compassionate God who is concerned for their weal and woes and who offers them an assured and holistic salvation. By placing their faith in God, the poor and marginalized people are discovering their true selves and are saved/liberated. This assured salvation (certitudo salutis), which is a total liberation of the physical and spiritual world, becomes, in turn, the motivational energy for capital development. The Zion Christian Church (ZCC) soteriological predicament stands at this juncture. Through processes of syncretization and purification, ZCC has managed to deconstruct the European/North American and African Traditional Religions soteriologies to construct a pure soteriology that is relevant to the socio context of its adherents. ZCC deconstructs these soteriologies by broadening, for example, the classic Christian soteriogical theory of Christus Victor in her notion of sin, death and the devil and the African traditional soteriological notion of uBuntu and spirit-power. The purity, or holistic salvation, generated out of these processes serves as grounds for identity and economic empowerment of its adherents. With a holistic salvation that centers on healing, personal integrity and spiritual power, ZCC members have been able to achieve considerable success in the labour market by becoming an army of potential employees. They have also distinguished themselves in their work ethic, where they are seen as hardworking, disciplined, obedient and sober. Empowering its adherents economically through a religious soteriology, the ZCC has become an example of a trend that is shaping the Global South and is reviving the interest of social scientists and theologians to further investigate the impact of religious and theological formulations on the economic conduct of individuals. / Theology / D. Th. (Theological Ethics)

Self-assembled monolayers and surface-initiated polymer, or polymer brushes, have attracted attention as they form dense layers with much higher structural order than bulk or solution polymers. Another field of research which has emerged over the last two decades is the field of organic and polymer electronics. In this field molecular order and surface modification are of major influence on the device performance, hence that both self-assembled monolayers as polymer brushes have been investigated to find applications in organic electronic devices. After an introduction into the field self-assembled monolayers, polymer brushes and organic electronics, the first part of this thesis focusses on three applications of surface modification techniques for applications in devices. Alignment of the active material is crucial for high mobilities in organic electronics. Chapter 2 discusses the synthesis of a liquid crystalline surface-initiated polymer and its application to induce strong homeotropic alignment. The alignment is homogeneous over large areas and can be patterned by combining the polymerization with soft lithographic techniques. Mobilities of organic electronic materials can also be strongly influenced by dopants in the material. In field-effect transistors the positioning of the dopant is thought to be crucial, as the conductance predominantly takes place in only a small channel near the dielectric interface. In chapter 3 dopant functionalized monolayers and polymer brushes are presented which enable the localized deposition of dopants in the channel of organic transistors. It is shown that the mobility of charges and hence the device performance is affected by the introduction of this dopant layer. Polymer brushes have been suggested for the fabrication of highly ordered semiconducting polymers. In chapter 4 the use of a thiophene functionalized polymer brush is shown, that can be used as a template for the subsequent growth of highly conjugated surface grafted polythiophene layers. Thick polythiophene layers are obtained, that are low in roughness and show photoluminescence and polychromism upon doping. The second part (chapter 5 and 6) of this thesis presents new techniques for surface polymerizations. It is attractive to investigate reduction of reactor volume for polymer brush growth. Chapter 5 discusses a method to achieve volume reduction by back-filling the superfluous volume with beads. It is found that this influences the polymerization kinetics significantly. The combined advantages of less volume and enhanced reaction speeds enable reduction of the total amount of monomer needed by up to 90%. Chapter 6 presents a controlled way to convert initiators for atom transfer radical polymerization into initiators for nitroxide mediated polymerization. In this way mixed polymer brushes and block co-polymer brushes become accessible. This combination makes it an attractive tool to fabricate complex polymer architectures. The technologies used in this thesis show that the synthesis of polymer brushes enable the fabrication of complex architectures without the wastes normally associated with surface-initiated polymers. Combined with several functionalized polymer brushes with properties that enhance order, influence mobility or serve as template for the growth of surface attached conjugated polymers this shows the high potential for the application of surface-initiated polymers in organic electronics.

Le but de ce travail de thèse est le développement d'un outil miniaturisé basé sur la millifluidique en goutte qui permet de synthétiser et d'étudier en toute sécurité des réactions de polymérisation dans des conditions difficiles ou «extrêmes».À cette fin, le réacteur de polymérisation a été réduit à la taille d'une gouttelette de quelques microlitres. A cette échelle, le microréacteurs goutte a un rapport surface sur volume plus élevé que ceux qui sont couramment obtenus avec des réacteurs discontinus classiques (~ 1500 par rapport à 10). Cette surface importante permet le transfert de chaleur efficace entre le milieu intérieur de la gouttelette (où la réaction chimique a lieu) et le milieu externe, qui est chimiquement inerte. Ici, contrairement à une approche monophasique, les caractéristiques clés d'une goutte miniaturisés permettent : (1) les gouttelettes de haute viscosité interne peuvent circuler normalement sans boucher le canal et (2) la dispersion due à la convection et la diffusion est éliminé car les réactifs sont compartimentées dans les gouttelettes. Comme toutes les gouttelettes se déplacent à la même vitesse, elles ne coalescent pas et il n'y a pas de distribution du temps de résidence. Ceci est particulièrement important étant donné que la viscosité dans des réactions de polymérisation peut augmenter à des milliers de centipoises ou même plus dans le cas des processus de gel.L'utilisation de gouttes comme microréacteurs circulant dans un tube chauffé (1/8’’ dext et 1/16’’ dint) peut permettre d’observer rapidement et en toute sécurité des réactions de polymérisation à différentes conditions. Nous avons choisi d'utiliser des conditions expérimentales où le processus de polymérisation est rapide et exothermique et/ou la viscosité peut être un problème. L'acide acrylique à faible pH et à concentrations élevées est donc un bon candidat pour obtenir un tel comportement. La composition des gouttelettes dépendant uniquement des débits, il est facile d’étudier différentes conditions expérimentales, y compris celles qui ne pouvaient pas être observées dans des réacteurs discontinus conventionnels (i.e. les concentrations de monomère et températures élevées, 40% massique et 90°C).Par ailleurs, couplé avec des systèmes appropriés d'analyse, des données cinétiques de base peuvent être obtenus en ligne à travers la paroi du tube transparent. En utilisant la spectrométrie Raman et l'équivalence temps-espace qui est spécifique à l'utilisation de dispositifs micro-et millifluidique à base de gouttes, nous avons été capables de suivre la conversion du monomère en fonction du temps. Ainsi, nous avons obtenu une cinétique d'ordre 4/3 en fonction de la concentration initiale en monomère et une demi-dépendance avec la concentration initiale de l'amorceur. Nous avons également pu mesurer une énergie d'activation globale de la vitesse de polymérisation entre 68°C et 90°C.En conclusion, la millifluidique et goutte semble être une approche prometteuse pour le criblage haut débit, l’analyse, et l’obtention de données cinétique de base en synthèse de polymères. / The aim of this thesis work is the development of a miniaturized droplet-based millifluidic tool which allows to safely synthesize and investigate polymerization reactions in harsh or “extreme” conditions.For this purpose, the polymerization reactor was reduced to the size of a droplet of a few microliters. At this scale, the droplet microreactor has a surface to volume ratio higher than those commonly obtained with conventional batch reactors (~1500 compare to 10). This important surface allows efficient heat transfer between the internal medium of the droplet (where the chemical reaction takes place) and the external one, which is chemically inert. Here, in contrast to single-phase flows, other key characteristics to a miniaturized droplet-based approach consist in: (1) droplets can manage high internal viscosity issues without plugging the channel and (2) dispersion due to convection and diffusion is eliminated because the reactants are compartmentalized within droplets. Since all droplets move at the same speed, they do not coalesce and there is no residence time distribution. This is particularly important since viscosity in polymerization reactions can increase to thousand of centipoises or even higher in the case of gel processes.The use of droplets as batch microreactors flowing within a heated tube (1/8 in. o.d. and 1/16 in. i.d.) can allow investigating quickly and safely polymerization reactions at different conditions. We choose to use experimental conditions where fast and exothermic polymerization process occurs and/or viscosity can be an issue. Acrylic acid at low pH and high concentrations is hence a good candidate to obtain such behavior. Since droplet composition depends only on flow rates, it was easy to screen different experimental conditions, including those which could not be used in conventional batch reactors (i.e., high monomer concentrations and temperatures; 40% w/v and 90 °C).Moreover, coupled with appropriate and sensitive analytical systems, basic kinetic data can be obtained in line through the wall of the transparent tube. By using Raman spectrometry and the time-space equivalence which is specific to the use of droplet-based micro- and millifluidic devices, we were capable to monitor molar conversions and monomer concentrations as a function of time. Thus, we verified the 4/3 order kinetics in initial monomer concentration and a 1/2 dependence in initial initiator concentration. We also able measured the overall activation energy for the rate of polymerization between 68°C to 90°C.In conclusion, droplet-based millifluidics seems to be a promising high throughput screening approach for investigating kinetics and possibly tailoring polymer properties.

L'objectif de ces travaux était de mettre au point une nouvelle voie de modification de la silice comme renfort d'élastomères silicones. La polymérisation par ouverture de cyclosiloxanes anionique (POCA) amorcée directement à partir de la silice dispersée en phase aqueuse a été réalisée. Les caractéristiques des silices utilisées dans cette étude ainsi que leur comportement en dispersion aqueuse ont tout d'abord été étudiés. La silice affiche des groupements silanolates à la surface de la silice pour des pH supérieurs au point de charge nulle. A pH 7, ces groupements silanolates en surface sont capables d'amorcer une polymérisation des cyclosiloxanes, et pas en suspension aqueuse. L'influence du contre-ion et de sa concentration sur le greffage obtenu s'est avérée primordiale, en complément des propriétés adsorbantes de la silice via les liaisons siloxanes. Les silices obtenues par ce nouveau procédé ont fait l'objet d'analyses poussées par thermogravimétrie, fragmentation-CPG, 29Si RMN simple impulsion et pyrolyse CPG-SM dans le but de décrire précisément la conformation du greffage. Le procédé a été transféré à plus grande échelle pour permettre la production d'importantes quantités de silice qui ont ensuite été incorporées dans une matrice silicone. Des limites de densités de greffage au-delà et en deçà desquelles la silice est mal dispersée dans le matériau ont été mises en évidence par traitement d'image. Les propriétés des élastomères ont été évaluées à partir de tests de dureté, de traction uniaxiale, de traction cyclique et de résistance à la déchirure dans le but d'étudier l'influence du greffage (conformation et groupements vinylés) sur le renforcement. / This work deals with a new way of modifying silica surface in a view to reinforce silicone elastomers. The surface-initiated ring-opening-polymerization (Si-ROP) of cyclosiloxanes was performed directly from the surface of silica dispersed in water. The characteristics of silica used in this study and their behavior in aqueous dispersion were first studied. For pH higher than the Point of Zero Charge, silica presents silanolate groups at its surface that are able to initiate the ROP of cyclosiloxanes from the surface, and not in aqueous suspension. The influence of the counter-cation and its concentration proved to be essential, in addition to silica's adsorbing properties. Modified silicas obtained by this new process were deeply analyzed by thermogravimetric analyses (TGA), fragmentation-GC, simple impulsion 29Si RMN and pyrolysis GC-MS in order to describe precisely the grafting conformation. The polymerization process was then scaled up to produce higher quantities of modified silica, which were incorporated in a model silicone formulation. Highest and lowest grafting densities tended to poor silica dispersions, as shown by image treatment. Hardness tests, uniaxial tensile and cyclic tests and tear resistance tests were performed in order to evaluate the influence of the grafting (conformation and vinylated groups) on silicone elastomers properties.

Globalization in the past few decades has been marked by increased mobility of highly skilled workers from one country to another. Even though self-initiated expatriation is a widespread phenomenon, it is a relatively under-researched phenomenon in the academic literature, especially in an organizational context. Existing literature shows that not all individuals are equally suited to embark on a new life in another country, and self-initiated expatriates (SIEs) could be particularly susceptible to failure since they have no support from a home organization. This study was designed to investigate the experiences of self-initiated professional expatriates and the effect it had on their work performance. The purpose was to understand how their organizational and social experience affected their cross-cultural adjustment process and in turn affected their individual work performance. The researcher used a qualitative method using semi-structured interviews, observations, and documents with ten self-initiated expatriates. This study contributed to the expanding literature on the experiences of self-initiated expatriates, specifically how different support systems affected cross-cultural adjustment and individual work performance.

Knowledge of radical initiated grafting was summarized in theoretical part. It also contains a part about adamantane, its derivatives and a study of their use in polymer chemistry. In experimental part radical grafted polypropylene was prepared in batch mixer Brabender at 185 and 195 °C, 40 RPM and reaction time 5 min. Initiator 2,5-dimethyl-2,5-bis(tert-buthylperoxy)hexane (Trigonox 101) in concentrations between 0,2 – 4 wt % was used. 1-vinyladamantane was chosen as a monomer and its concetration ranged from 0,75 to 2,24 wt %. Mechanical properties of prepared samples were tested. Sample with content of initiator 0,2 wt % and monomer 1,4 wt % showed increase in notch toughness by 56,3 %, strength by 8,7 %, ductility by 11,5 % and decrease in MFR (230 °C; 2,16 kg) by 29,7 %. Values of torque indicated grafting reactions which couldn’t be proven by use of FTIR method so more suitable methods have been proposed.

ABSTRACT Mixed function oxygenase system participates in biosynthesis of endogenous and metabolism of exogenous substances (e.g. drugs or chemical procarcinogens) in an organism. Substrates are biotransformed by terminal oxygenases - cytochromes P450 (P450). Catalytic properties of certain P450s (e.g. studied isoform 2B4) are altered in the presence of a redox partner - cytochrome b5 (cyb5). Both cytochromes are anchored by hydrophobic domains in a lipid membrane of endoplasmic reticulum whereas their catalytic domains are exposed to cytosol. Two zero-length cross-linking approaches were employed to extend present knowledge of P450 2B4 and cyb5 protein structure and protein-protein interactions: (1) interlinking of carboxylate and primary amine groups of amino acids by water soluble 1- ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), and (2) photo-initiated cross-linking by photo-labile methionine analog (pMet), which links to any amino acid after activation by UV-irradiation, either in hydrophilic or hydrophobic environment. pMet was incorporated to methionine site(s) of cyb5 during recombinant expression in E. coli, which was carried out in limit medium supplemented with amino acid analog. Optimization of experimental conditions led to ~20-30% substitution of the natural amino acid. Covalent...

Self-assembled microsphere monolayers (SMMs) hold significant promise for micro- and nanopatterning. Here we exploit, for the first time, SMMs as stamps for microcontact printing (μCP) and demonstrate this to fabricate patterned initiator templates that can subsequently be amplified into polymer brushes by surface initiated atom transfer radical polymerization (SI-ATRP). SMM stamps avoid the need for expensive and sophisticated instrumentation in pattern generation, and provide a broad range of accessible surface chemistries and pitch size control.

Research has identified the important role that effective parent-adolescent communication about sex and relationships signifies in reducing the chances of adolescents engaging in risky sexual behaviour. However, many parents find it difficult to discuss issues related to HIV prevention at family level because HIV prevention is inherently linked to sex, which is still regarded as a taboo in some countries, including the country of the study, Swaziland. In addition to cultural barriers related to effective parent-adolescent communication, parents seem to lack the knowledge, approach as well as the confidence regarding communication about sex and relationships. The purpose of the study was to use appreciative inquiry (AI) to engage parents of adolescents in the design of interventions to prevent HIV among adolescents in Swaziland. Non-probability, purposive sampling was used to select parents of adolescent children (10-19 years) attending school at the two purposively selected high schools in Manzini. Twenty-four (24), 23 female and 1 male parents took part in AI. Participatory action research was conducted to involve participants actively in the process of initiating interventions for preventing HIV among adolescents. The process was guided by appreciative inquiry. Data was collected by means of appreciative interviews, comprising paired and focus group interviews according to different phases of the 4-D cycle of AI. Thematic analysis of data was done throughout the 4-D cycle of AI. The themes that emerged from appreciative stories of exceptional experiences shared during the discovery phase were perceived gains and open communication. The findings of the dream phase included expressed wishes for open parent-adolescent sexual health communication, support for parents and a community of HIV free adolescents. In the design phase, parents constructed and initiated interventions for effective parent-adolescent sexual health communication and parental comfort with communication about sex. In the destiny phase, parents made statements, which were based on what they committed to do to prevent HIV among adolescents. / Lucwaningo lukhombisa bumcoka bekukhumisana kahle kwemtali nemtfwana loyinsha ngetindzaba tebundlelwane bebantfu labatsandzanako netekulalana kuze kutsi kunciphe kutsi intsha ingabi sengotini yekutfola ligciwane HIV. Kodvwa kubatali labanyenti kulukhuni kukhulumisana nentsha ngetindzaba tekutivikela kuHIV emakhaya ngoba kukhuluma ngalendzaba kufaka ekhatsi tekulalana lokuselichilo kukhuluma ngako emaveni lamanyeti lokufaka ekhatsi leSwatini lapho kwetiwa khona lolucwaningo. Lokunye lokuvimbela kutsi batali bangakhulumi ngalendzaba ngaphandle kwekutsi kulichilo, kutsi batali baswele lwati nekutsi abati kutsi bangayingena njani intsha, kanye nekutsi abatetsembi kutsi bangakhona kukhuluma ngebudlelwane bebantfu labatsandanako kanye nekulalana. Injongo yalolucwaningo bekukusebentisa indlela yekubuketa lokuhle kubatali labakwentako mayelana nekukhulumisana nentsha kuze kutsi bakhe tindlela letingito tokutivikela intsha kuHIV Eswatini. Indlela labakhetfwe ngayo batali labangene lolucwaningo bakhetfwe ngokutsi banebantfwana bentsha labaneminyaka lelishumi kuya kulabo labanelishumi nemfica labafundza etikolweni letimbili letiphakeme letikhetsiwe kaManzini. Babangemashumi lamabili nesine batali labatfolakala kungenela lolucwaningo. Batali babamdzibi munye nebacwaningi kuloluhlelo lokuhlela tindlela tekuvikela iHIV kubantfwana labayintsha. Kwakusetjentiswa tindlela letibuka lokuhle lokwetiwe batali. Imibuto beyihlose kubuta ngalokuhle kodvwa. Imivo yebatali yatfolakala nekutsi bacale babutana bodvwana besebakhulunyiswa baticagogwana ngekwehlukana kwaletigaba letine talolucwaningo. Kuhlanganisa kwemivo kwentiwa ngekutsi kubuketwe tingcikitsi kutotonkhe tigaba talolucwaningo. Tingcikitsi letaphuma kuletingcoco esigabeni sekucala lapho bebakhuluma ngetikhatsi letinhle letabayimphumelelo lapho bebakhumisana nentsha ngekulalana nangeHIV, batsi bevakunemphumelelo nekubhobokelana ekhatsi kwebatali nebantfwana. Ngalesikhatsi sesigaba sekubeka emaphupho abo basho batsi bafisa kube nekubhobokelana phakatsi kwebatali nentsha mayelana nekulhulumisana ngekulalana. Lokunye labakufisile kutsi basekelwe basitwe ngekutsi intsha ikhulunyiswa njani. Ngesikhatsi sesigaba sesitsatfu sekubuketwa kutsi kungentiwani kutsi batali nebantfwana bakhulumisana ngetindzaba tekutsandzana kanye nekulalana batali babhala imivo labo. Ngemuva kwaloko benta tivumelwano tekutsi batakwentanjani uma sebabuyela emakhaya kuze bakhone kuvikela bantfwana bentsha kuHIV. / Health Studies / D. Litt. et Phil. (Health Studies)