This dissertation presents the synthesis of a series of well-defined multiresponsive hydrophilic ABA linear triblock copolymers and the study of their aqueous micellar gels. By incorporating a small amount of stimuli-responsive groups into thermosensitive outer blocks of ABA triblock copolymers, the lower critical solution temperatures (LCST) of thermosensitive blocks can be modified by external stimuli. Consequently, the sol-gel transition temperatures (Tsol-gel) of their aqueous solutions can be altered. Chapter 1 describes the synthesis and solution behavior of a series of thermo- and light-sensitive triblock copolymers, poly(ethoxytri(ethylene glycol) acrylate-co-o-nitrobenzyl acrylate)-b-poly(ethylene oxide)-b-poly(ethoxytri(ethylene glycol) acrylate-co-o-nitrobenzyl acrylate), with different contents of light-responsive o-nitrobenzyl groups. Aqueous solutions of these block copolymers with a 10.0 wt% concentration exhibited thermo-induced sol-gel transitions. Upon UV irradiation, the hydrophobic o-nitrobenzyl groups were cleaved, resulting in an increase in the LCST and consequently gel-to-sol transitions. The UV-irradiated solutions again underwent temperature-induced sol-gel transitions but at higher temperatures. The change of Tsol-gel was, in general, larger for the copolymer with a higher o-nitrobenzyl content after UV irradiation. Chapter 2 presents the synthesis of thermo- and enzyme-responsive ABA triblock copolymers, poly(ethoxydi(ethylene glycol) acrylate-co-4-((dihydroxyphosphoryl)oxy)butyl acrylate)-b-poly(ethylene oxide)-b-poly(ethoxydi(ethylene glycol) acrylate-co-4-((dihydroxyphosphoryl)oxy)butyl acrylate), and the enzyme-induced formation of thermoreversible micellar gels from their moderately concentrated aqueous solutions at 37 °C. The dephosphorylation by acid phosphatase decreased the LCST of thermosensitive outer blocks from above to below 37 °C. The enzyme-induced gelation of 7.9 wt % aqueous polymer solutions at pH 4.4 was monitored by rheological measurements. The Tsol-gel decreased and the gel strength increased with the increase of reaction time. The gels formed were thermoreversible. Chapter 3 presents the synthesis of two thermo- and pH-sensitive tertiary amine-containing ABA triblock copolymers and the sol-gel transitions of their aqueous solutions with a 10 wt% concentration at different pH values. Chapter 4 describes the use of reversible addition-fragmentation chain transfer (RAFT) polymerization for the synthesis of well-defined thermosensitive polymethacrylates and polyacrylates. Eight chain transfer agents were synthesized. The RAFT polymerizations of alkoxyoligo(ethylene glycol) (meth)acrylates using these chain transfer agents were well controlled, producing well-defined polymers. A summary of this dissertation research and future work are presented in Chapter 5.

The research described covers fundamental studies of environmentally-responsive microgel-based thin films as a function of film architecture, microgel chemistry, film thickness, and environmental stimulus. Studies of multi-layer microgel thin films were conducted primarily using atomic force microscopy (AFM), quartz crystal microgravimetry (QCM), and surface plasmon resonance (SPR), each of which probed different aspects the film architecture as a function of pH of the environment around the film. Binary thin films were constructed by changing the ratios and composition of the microgels in solution to create multi-functional thin films for surface modification applications and were studied using AFM. The basic understanding of how these components create films at surfaces gives us insight into how the films perform and will allow for greater diversity without the guesswork. The morphology of films created from microgels with a degradable cross-linker was examined by AFM as a function of degradation of the particles structure. This thesis focuses mainly on very thin microgel films (<5 layers) studied using QCM, SPR, and AFM. Additional studies involving the characterization of semi-soft colloidal paint-on photonics are discussed in Appendix A.

<p>  </p> <p>Social justice researchers and practitioners have beckoned post-secondary institutions to provide inclusive and culturally responsive instructional practices that promote students' sense of belonging and empowerment. However, little research has demonstrated how competent intercultural behaviors can connect to one's integration of culturally responsive teaching. Therefore, this explanatory sequential mixed-methods study examined the interplay between these components within a distinguished undergraduate peer learning program, Supplemental Instruction (SI). Undergraduate SI leaders’ behaviors were examined for their intercultural competence level, potential influencers, and valued commitment to diversity and inclusion. This study was supported and guided by Hammer’s (2012) Intercultural Development Continuum (IDC) and Gay's (2018) Culturally Responsive Teaching (CRT) practices. Quantitative data were collected using Hammer's (2012) Intercultural Development Inventory (IDI), and qualitative data were in the form of interviews and analyses of leaders' session plans. The findings revealed that participants overestimated their intercultural competence. Relatedly, participants expressed concerns of uncertainty beyond solely acknowledging diversity and addressing intercultural insensitivity. Curricular and co-curricular programming were potential influencers to the leaders' intercultural competence knowledge (i.e., cultural self-awareness, culture-general, and culture-specific). Additionally, implications include recommendations for higher education administrators' initiatives for more inclusive and culturally responsive peer-learning programs. </p>

Since the third-generation’s mobile telephony was introduced, the use of the Internet changed significantly. Websites can nowadays be viewed from a wide range of devices that differ in type and size. This puts a demand on the design of web pages because the page should be equally useful regardless of the type of device used to view the page. Responsive web design is a design method that strives towards solving this problem by allowing web pages to customize their visual representation based on the medium used to interact with them. Although it is a well-used tool in web development, it is relatively unexplored from a technical, aesthetic and functional perspective. The goal of this thesis is to improve the situation by exploring the possibilities and limitations of responsive web design in relation to the above perspectives. To achieve this, common definitions of this approach were collected, together with an implementation of a responsive product. To give structure to the analysis, the development process followed the Double Diamond approach together with two experiential qualities, fluidity and naturality. By using media queries together with scalable units in the implementation, a fully responsive portfolio website was created. The creation of the product gave room for understanding possibilities and limitations of responsive web design. The encountered problems in this thesis, such as detecting different types of devices, concludes that responsive web design is yet not a fully developed approach and contains problems that limit the implementation.

This thesis addresses how leaders find themselves doing something even when they don't know what to do. It is based on my own practice as an experienced team leader and it deals with questions of action, time, identity and leadership. A classic understanding of action usually reflects an expectation of a rational means-ends relationship where actions are designed and applied by individuals to reach well-defined goals within a certain context and within a certain time. In contrast, in this thesis, I describe acting as a much more complex process, as something becoming, as a patterning of activities involving multiple actors in a continuous and complex interweaving of relationships. I describe my experience of leading a team of consultants in international development projects where I inquire into how we often find ourselves acting into uncertainty even when we are not at all sure what to do. Adopting the theory of complex responsive processes of relating, which combines insights from the complexity sciences, social psychology and process sociology, I have come to see acting in our projects as complex, unpredictable, emerging themes and patterns of dialogues between colleagues, clients and other actors, rather than as an activity undertaken by an individual such as a team leader. I do not have an outside position to acting in a project as I am fully involved in the process while this paradoxically influences me at the same time. I argue that acting is related to identity, which can be understood as a sense of self, a person's moral self-interpretation which has a narrative structure and which is continuously being formed by (and is forming) one's acting. I argue that my experience of our practice may be explained by the pragmatists' understanding of acting based on actual lived experience where the means paradoxically become our 'ends-in-view' and vice versa, meaning that we do not just try to maintain a theoretical, future goal but move forwards towards what is practically possible, what we find useful and what makes sense in the present. Acting happens in a living present, meaning that we understand the present through our interpretation of the past as well as our expectation of the future, and we construct this living present as something that works for us when we pursue our collective aims and interests. In the process of acting, there is an arrow on time, meaning that what has been said cannot be unsaid, wherefore it is important to reflect on the perspective of 'ends-in-view' and to understand how acting into a situation may reveal new opportunities. The thesis contributes to knowledge within my profession as an original invitation to think differently about two aspects: first, seeing acting in a project with a much more processual, temporal and encompassing understanding where action is not located in an individual; second, understanding how acting is influenced by one's identity, a sense of self, which is paradoxically being formed by the acting at the same time. Further, the thesis identifies sociality, being different things at the same time (Mead, 1932/2002), as a new aspect in the theory of complex responsive processes of relating (Stacey, Griffin, & Shaw, 2000), recognising its significance in the process of understanding of how novelty occurs. The thesis contributes to my practice in terms of an increased reflexivity and acceptance that a team leader cannot determine outcomes in advance; that leadership is a complex process involving many actors; and that observing ends-in-view may create new and surprising ways forward. I find that these insights can lead to an increased acceptance of how we can act under conditions of uncertainty.

Talent management is an organisational process aimed at maximising the benefit gained from the organisation's workforce, mostly by assessing the future potential of senior organisational members to fill key positions based on their proportional contribution to the business. Despite the increasing prevalence of talent management, evidence is accumulating to indicate an extremely low success rate of just 20-25% in predicting high performers. While talent management continues to address a growing business need, a better understanding of the process may help to refine its practice. The underpinning assumptions of the practice of talent management are that organisations are systemic and linear, and that talent management must produce a single answer identifying what it means to be a 'talent' in any specific circumstance. As a profession, talent management also maintains a fantasy of control: the expectation that assessed individuals will indeed behave as anticipated, and that stated targets will remain unchanged. As a progressive and trending HR process, talent management's close connection to organisational power relations and political dynamics is rarely acknowledged. The emotional toll on assessed senior executives, as well as potential ramifications for their colleagues, is also often overlooked, despite the significant implications for individual careers and broader inferences of inclusion-exclusion inherent in the process of talent selection. Talent management practitioners and scholars tend not to consider the impact on individuals of inaccurate assessments and mistaken decisions. As a talent manager practitioner who decrees the fate of individuals, such glaring oversights provoked in me an acute ethical anxiety that drove this research. This work offers a critical perspective on the practice of talent management - in particular, the process of judgment involved in the assessment of 'high potentials' and the potent dynamics of inclusion in/exclusion from the talent group. Having witnessed first-hand the inconsistency between apparently robust predictions (based on best practice) and subsequent outcomes, I began this research with strong feelings of ambivalence towards my practice of 25 years and my prospering business of 10 years. The critical perspective of the current study took shape within the research framework, which is based on the philosophy of pragmatism and the complex responsive process of relating that draws on it, as well as on process sociology and complexity sciences. The research methodology insists that scholars take their own direct experience seriously, collect their raw data through writing narratives, and then exercise reflection and reflexivity both as individuals and as part of the Doctor of Management (DMan) learning community. The narratives 'translate experience so that it is meaningful to the reader' (Cunliffe, 2010, p. 228). Applying this innovative approach not only to my research, but also to my professional practice, has led me to challenge the most fundamental assumptions of talent management. I now have a deeper and more nuanced understanding of the process of judgment at its core, and have developed a new way to approach and implement this process within my work. This thesis culminates in three main arguments describing talent management from a new perspective, as well as redefining the role and degree of involvement of talent management consultants. First, the central process of judgment emerged not as an objective analysis communicated in a unidirectional, linear way from the assessor to the assessed, but rather as a relational and social process that involves shifting power relations and an inclusion-exclusion dynamic influenced by many unpredictable factors. Second, from the perspective of the research framework, the assessor can no longer be seen as an objective observer, but must be regarded as a participant who is simultaneously both involved and detached and who must rely on their practical judgment. Talent management's traditional promise of future-oriented focus and reliable predictions is illusory, given that all participants are continuously merging their ongoing experiences to spontaneously co-create the future in unpredictable ways. . Understanding that the assessment process is not a simple numerical exercise (ranking individuals on various scales) and that no single truth can be obtained through an assessment process (since assessment results are co-created with all participants in the process) has eased my ethical concerns and enabled me to continue practising my profession with confidence, by taking a fresh viewpoint of what it is that I am doing. It is my hope that other talent management practitioners will find these insights useful and generalisable, and valid to their own practice - extrapolating from the local to the global.

Le but de cette thèse de doctorat était de concevoir des brosses de polymères stimuli-sensibles afin de contrôler dynamiquement les interactions adhésives entre une cellule et son substrat.Pour cela, nous avons utilisé la polymérisation radicalaire par transfert d'atomes (ATRP) initiée en surface, et sa variante permettant de régénérer in situ le catalyseur de polymérisation (ARGET-ATRP), pour préparer des brosses thermo-sensibles de poly(N-isopropylacrylamide) (PNIPAM). Les deux méthodes ont été appliquées pour différentes densités surfaciques et temps de polymérisation, et les cinétiques de croissance de la brosse à l'aide des deux protocoles ont été étudiés. Une croissance de chaîne bien contrôlée a été observée avec le protocole ARGET-ATRP, mais pas avec la méthode ATRP. Le protocole testé ci-dessus a été utilisé pour fabriquer des brosses de PNIPAM qui ont été patternées par l'intermédiaire d'une stratégie d'ablation aux UV profonds, afin de concevoir des substrats permettant de contrôler spatialement l'adsorption de protéines. Ces substrats ont montré d'excellentes propriétés adhésives, sont réutilisables et peuvent se stocker sur de longues périodes.Les changements conformationnels de brosses PNIPAM ont été sondés grâce à un dispositif original mis en place sur la base d'un microscope en réflexion à contraste d'interférences (RICM). La technique RICM a permis d'estimer la réponse optique des brosses en fonction de leur profil de hauteur, ce qui en fait un outil intéressant pour leur caractérisation. La réponse de la brosse a été étudiée en fonction de sa densité de greffage et de la longueur de chaîne. Les résultats ont fourni une preuve unique de l'existence d'un phénomène de séparation de phase verticale, donnant lieu à des changements structurels non-uniformes dans les brosses lors du passage de la température inférieure de solubilité du PNIPAM dans l'eau. Le RICM a été utilisé pour réaliser la tâche complexe d'estimer les paramètres moléculaires de la brosse et la compréhension de l'origine physique du phénomène d'hystérésis thermique dans une brosse de polymère.De nouveaux polymères stimuli-sensibles ont été synthétisés dans le but d'obtenir des systèmes d'intérêt pour les études biologiques en conditions physiologiques. Nous avons conçus différents co-polymères photo-thermo-sensibles à base d'acrylamides et d'acrylates. Les changements de conformation des polymères conçus ont été étudiés en détail en faisant varier la composition globale des monomères dans le système. Nous avons identifié une composition de ter-polymères dont les solutions aqueuses ont montré une séparation de phase à 37°C qui peut être réversible sous irradiation lumineuse, ce qui la rend compatible pour les études d'adhésion cellulaire. / The aim of the current Ph.D thesis was to design stimuli responsive polymer brushes in order to dynamic control cell-substrate adhesive interactions.For this purpose, Atom Transfer Radical Polymerization (ATRP) and Activators Regenerated by electron Transfer (ARGET)-ATRP were used in order to prepare thermo responsive Poly(N-isopropylacrylamide) (PNIPAM) brushes. Both the methods were applied under varying surface densities and polymerization times, and the kinetics of the brush growth using both the protocols was investigated. A well controlled chain growth was reported under ARGET-ATRP protocol, in contrast to the ATRP method. The above tested protocol was used to grow PNIPAM brushes that were patterned via deep UV photoablation strategy to design thermoresponsive patterned substrates for protein adsorption studies.The substrates showed excellent adhesive properties and reusability with long term storage capacity.The conformational changes of PNIPAM brushes, grown via the ARGET-ATRP protocol, were investigated using an original set-up based on Reflection Interference Contrast Microscopy (RICM). RICM allowed us to probe the optical response of the brushes as a function of their density profile, making it an interesting tool for brush characterization. The response of the brush was studied as a function of brush grafting density and chain length. The results provided a unique evidence for non-uniform structural changes within the brush thickness when the solvent temperature was varied across the Lower Critical Solution Temperature (LCST) of the polymer. RICM was employed to achieve the challenging task of estimating the molecular parameters of the brush and understanding the physical origin of the phenomenon of thermal hysteresis in a polymer brush.Stimuli Responsive Polymers, sensitive to non-invasive stimuli, were synthesized with an aim to address dynamic single cell adhesion studies at their physiological conditions. Free Radical Polymerization and ARGET-ATRP protocol were used to design two photo-thermo-responsive poly(DMA-AZAA) and poly(DMA-NIPAM-AZAAm) polymers. The conformational changes of the designed polymers were investigated at length by varying the overall composition of monomers in the system. The solutions of the DMA-NIPAM-AZAAm terpolymer showed a sharp phase separation at 37°C that could be reversibly switched under light irradiation, making it compatible for cell adhesion studies.

The aim of this research is to examine the role of practice in collaboration between designers and African craft producers in order to develop a different methodology for future exchanges that can be more sustainable and equitable. It looks to determine how craft and design practices can act as tools for communication and exchange, to examine how to foster meaningful collaboration when the relationship of those involved is inequitable and to develop a co-creation methodology for practice, capitalising on the differing skills, experiences and cultures of those involved. The research explores collaboration through making with two Cape Town based, craft businesses - Imiso Ceramics and Kunye - investigating the interactions that occur between the collaborators. A critical contextual review reveals the majority of such partnerships are instigated from the top down with an emphasis on product development. This study proposes that the focus is shifted to one that is human-centred, where the process of collaboration between the people involved is foregrounded. By strengthening the collaborative relationships and giving all participants an equal voice, the process becomes more productive, with product development an inherent result. Using a practice based, participatory design methodology, the work draws on the African notion of ubuntu, which speaks of people's interconnectedness. Applying the cross-disciplinary practices of all three collaborators, products are developed, provoking a dialogue that challenges the designer's role in the developing world. The research culminates in an exhibition of the journey, conversations, issues and outcomes that occurred throughout. The exhibition provides an opportunity to provoke a conversation with the stakeholders, listening to their experiences and gaining their feedback on the work presented. Practical exercises for participatory design in future cross-cultural, cross-disciplinary contexts are presented.

Ce travail de thèse s'inscrit dans un domaine de recherche actuellement en pleine expansion, celui des nanomatériaux stimulables. Il vise à concevoir de nouveaux matériaux biocompatibles et biodégradables par modification chimique contrôlée de polysaccharides pour le traitement de patients diabétiques. Le diabète est un problème de santé publique majeur qui affecte environ 250 millions de personnes dans le monde actuellement contre 30 millions il y a 20 ans. Cette maladie se traduit par un taux de glucose anormalement élevé dans le sang dû à un manque d'insuline. Cette protéine est habituellement injectée de manière sous-cutanée, 2 à 4 fois par jour. Les hydrogels/nanogels visés dans ce travail doivent donc être capables de libérer l'insuline en fonction du taux de glucose dans le sang. Ce projet comporte plusieurs volets : (i) la synthèse contrôlée de polysaccharides porteurs de groupements permettant la réticulation des polymères ainsi que des molécules sensibles au glucose , (ii) la synthèse et la caractérisation d'hydrogels et nanogels (en utilisant des liposomes comme nanoréacteurs). / This PhD thesis belongs to the area of stimuli-responsive materials, which have attracted a growing interest since several years. Its aim is to design biocompatible and biodegradable stimuli-responsive nanogels obtained from chemically modified polysaccharides to treat diabetic patients. These systems may be used to release insulin in a self-regulated manner. This common disorder of blood glucose regulation due to a lack of insulin is a major public health problem affecting about 250 millions of people in the world today, as compared to 30 millions twenty years ago. Patients diagnosed with insulin-dependent diabetes must take insulin by injecting themselves with a needle at least twice a day. The nanogels targeted in this work are thus expected to release insulin as a function of blood glucose concentration.This project will thus consist in the controlled synthesis of polysaccharides bearing cross-linkable groups and a sugar sensor. These biopolymers will be then used to prepare hydrogels and nanogels (using liposomes as nanoreactors).

abstract: Electronic devices based on various stimuli responsive polymers are anticipated to have great potential for applications in innovative electronics due to their inherent intelligence and flexibility. However, the electronic properties of these soft materials are poor and the applications have been limited due to their weak compatibility with functional materials. Therefore, the integration of stimuli responsive polymers with other functional materials like Silicon is strongly demanded. Here, we present successful strategies to integrate environmentally sensitive hydrogels with Silicon, a typical high-performance electronic material, and demonstrate the intelligent and stretchable capability of this system. The goal of this project is to develop integrated smart devices comprising of soft stimuli responsive polymeric-substrates with conventional semiconductor materials such as Silicon, which can respond to various external stimuli like pH, temperature, light etc. Specifically, these devices combine the merits of high quality crystalline semiconductor materials and the mechanical flexibility/stretchability of polymers. Our innovative system consists of ultra-thin Silicon ribbons bonded to an intelligently stretchable substrate which is intended to interpret and exert environmental signals and provide the desired stress relief. As one of the specific examples, we chose as a substrate the standard thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogel with fast response and large deformation. In order to make the surface of the hydrogel waterproof and smooth for high-quality Silicon transfer, we introduced an intermediate layer of poly(dimethylsiloxane) (PDMS) between the substrate and the Silicon ribbons. The optical microscope results have shown that the system enables stiff Silicon ribbons to become adaptive and drivable by the soft environmentally sensitive substrate. Furthermore, we pioneered the development of complex geometries with two different methods: one is using stereolithography to electronically control the patterns and build up their profiles layer by layer; the other is integrating different multifunctional polymers. In this report, we have designed a bilayer structure comprising of a PNIPAAm hydrogel and a hybrid hydrogel of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA). Typical variable curvatures can be obtained by the hydrogels with different dimensional expansion. These structures hold interesting possibilities in the design of electronic devices with tunable curvature. / Dissertation/Thesis / M.S. Chemical Engineering 2012