Bio and chemocatalysis for stereo and regioselective one-pot reaction applications

The development of cost efficient, selective and sustainable chemical processes for production of chiral building blocks is of great importance in synthetic and industrial organic chemistry. One way to reach these objectives is to carry out several reactions steps in one vessel at one time. Furthermore, when this kind of one-pot multi step reactions are catalyzed by heterogeneous chemo- and bio-catalysts, which can be separated from the reaction products by filtration, practical access to chiral small molecules for further utilization can be obtained. The initial reactions studied in this thesis are the two step dynamic kinetic resolution of rac-2-hydroxy-1-indanone and the regioselective hydrogenation of 1,2-indanedione. These reactions are then combined in a new heterogeneously catalyzed one-pot reaction sequence enabling simple recovery of the catalysts by filtration, facilitating simple reaction product isolation. Conclusively, the readily available 1,2-indanedione is by the presented one-pot sequence, utilizing heterogeneous enzyme and transition metal based catalysts, transferred with high regio- and stereoselectivity to a useful chiral vicinal hydroxyl ketone structure. Additional and complementary investigation of homogeneous half-sandwich ruthenium complexes for catalyzing the epimerization of chiral secondary alcohols of five natural products containing additional non-functionalized stereocenters was conducted. In principle, this kind of epimerization reactions of single stereocenters could be utilized for converting inexpensive starting materials, containing other stereogenic centers, into diastereomeric mixtures from which more valuable compounds can be isolated by traditional isolation techniques.

Microbiological and sensory evaluation of Jambu (Acmella oleracea L.) dried by cold air circulation

Abstract The aim of this study was to evaluate the microbiological and sensory quality of the Jambu (Acmella oleracea L.) in natura and dried by cold air, and the determination of its drying curve. The microbiological analysis were performed to Salmonella spp, the coagulase-positive Staphylococcus, and coliforms in the both Jambu samples, at 45 °C. Tacacá, the typical food dish of Pará state, Brazil, has showed good consumer global acceptance in the sensory evaluation of Jambu in natura (score of 8.00 ± 1.46) and dried (score of 8.67 ± 0.66). Both samples, Jambu in natura and dried by cold air, were by the current legislation regarding the microbiological aspects, this is the absence of Salmonella spp, coagulase-positive Staphylococcus <1×101 CFU/g, and coliforms <3 MPN/g, at 45 °C. Thus, considering sensory and health aspects, the commercialization of dried Jambu becomes viable, facilitating its transportation and handling, as well as for reducing its vegetable mass.

From epithelial to mesenchymal: regulation of invasive cancer cell motility

Metastasis is the main cause of death among cancer patients. In order to initiate the metastatic cascade cancer cells have to undergo epithelial-to-mesenchymal transition (EMT). In EMT epithelial cells lose their cell-cell and cell-extracellular matrix (ECM) contacts and become more motile. The expression of the transcription factor Slug and of the mesenchymal intermediate filament vimentin is induced during EMT. Vimentin is often overexpressed in malignant epithelial cancers but the functional role of vimentin remains incompletely understood. In addition, kinases such as AKT and ERK are known to be involved in the regulation of EMT and cancer cell motility but the mechanisms underlining their functions are often unclear. Integrins are heterodimeric receptors that attach cells to the surrounding tissue and participate in regulating cell migration and invasion. Changes in integrin activity are linked to increased cell motility and further cancer metastasis. The aim for my PhD studies was to investigate the role of cellular signalling pathways and vimentin in the regulation of cancer cell motility and EMT. Our results revealed that in prostate cancer the downregulation of AKT1 and AKT2, but not AKT3, induces activation of cell surface 1-integrins leading to enhanced cell adhesion, migration and invasion. In addition, our findings demonstrated a reciprocal regulatory interaction between vimentin and ERK2 facilitating ERK-mediated phosphorylation of Slug at serine-87 (S87) in breast cancer. Surprisingly, Slug S87 phosphorylation is dispensable for E-cadherin repression but essential for the induction of vimentin and Axl expression in early onset of EMT. Our findings reveal previously unknown mechanistic information of how prostate and breast cancer cell motility and disease progression is regulated

Influencing Perceived Agency: A Study into User Experiences in Digital Interactive Storytelling

User experience is a crucial element in interactive storytelling, and as such it is important to recognize the different aspects of a positive user experience in an interactive story. Towards that goal, in the first half of this thesis, we will go through the different elements that make up the user experience, with a strong focus on agency. Agency can be understood as the user’s ability to affect the story or the world in which the story is told with interesting and satisfying choices. The freedoms granted by agency are not completely compatible with traditional storytelling, and as such we will also go through some of the issues of agency-centric design philosophies and explore alternate schools of thought. The core purpose of this thesis is to determine the most important aspects of agency with regards to a positive user experience and attempt to find ways for authors to improve the overall quality of user experience in interactive stories. The latter half of this thesis deals with the research conducted on this matter. This research was carried out by analyzing data from an online survey coupled with data gathered by the interactive storytelling system specifically made for this research (Regicide). The most important aspects of this research deal with influencing perceived agency and facilitating an illusion of agency in different ways, and comparing user experiences in these different test environments. The most important findings based on this research include the importance of context-controlled and focused agency and settings in which the agency takes place and the importance of ensuring user-competency within an interactive storytelling system. Another essential conclusion to this research boils down to communication between the user and the system; the goal of influencing perceived agency should primarily be to ensure that the user is aware of all the theoretical agency they possess.

Geneerisen karttakomponentin kehitys: Tapaustutkimus kohdeyrityksen tuotteissa

Erilaisten paikkatietoon ja karttoihin perustuvien palveluiden määrä on viime vuosina kasvanut suuresti. Eräänä mahdollistajana tähän lienee Euroopan Unionin Inspire-direktiivi, jonka tavoitteena on tehostaa paikkatietoaineistojen käyttöä, laajentaa viranomaisten välistä yhteistyötä, sekä edistää monipuolisten kansalaispalveluiden syntymistä. Toisena tekijänä lienee mobiiliverkkojen tiedonsiirtokapasiteetin kasvu. Tämä diplomityö keskittyy geneerisen karttakomponentin kehitykseen. Työssä tutustutaan erilaisiin paikkatiedon välityksessä käytettäviin tiedonsiirtotekniikoihin ja paikkatiedon visuaalisen esityksen mahdollistaviin työkaluihin. Tekniikoiden esittelyn jälkeen selvitetään mitä käytettävyydellä ja geneerisyydellä tarkoitetaan kirjallisuuslähteitä apuna käyttäen. Työn seuraavassa vaiheessa toteutetaan prototyyppi uudelleenkäytettävästä karttakomponentista, sekä selvitetään hyvä tallennusratkaisu erilaisille kartalle tehtäville merkinnöille. Viimeisessä vaiheessa analysoidaan toteutusta ja valittuja ratkaisuja. Työn tuloksina saadaan uudelleenkäytettävän karttakomponentin prototyyppi sekä yrityksen tuotteisiin sopiva tallennusratkaisu karttamerkinnöille. Lisäksi prototyypin analysoinnista saatavat tulokset edesauttavat paremman tuotantoversion kehittämisessä.

University students’ regulation of learning and text processing – examples from medical and teacher education

The general aim of the thesis was to study university students’ learning from the perspective of regulation of learning and text processing. The data were collected from the two academic disciplines of medical and teacher education, which share the features of highly scheduled study, a multidisciplinary character, a complex relationship between theory and practice and a professional nature. Contemporary information society poses new challenges for learning, as it is not possible to learn all the information needed in a profession during a study programme. Therefore, it is increasingly important to learn how to think and learn independently, how to recognise gaps in and update one’s knowledge and how to deal with the huge amount of constantly changing information. In other words, it is critical to regulate one’s learning and to process text effectively. The thesis comprises five sub-studies that employed cross-sectional, longitudinal and experimental designs and multiple methods, from surveys to eye tracking. Study I examined the connections between students’ study orientations and the ways they regulate their learning. In total, 410 second-, fourth- and sixth-year medical students from two Finnish medical schools participated in the study by completing a questionnaire measuring both general study orientations and regulation strategies. The students were generally deeply oriented towards their studies. However, they regulated their studying externally. Several interesting and theoretically reasonable connections between the variables were found. For instance, self-regulation was positively correlated with deep orientation and achievement orientation and was negatively correlated with non-commitment. However, external regulation was likewise positively correlated with deep orientation and achievement orientation but also with surface orientation and systematic orientation. It is argued that external regulation might function as an effective coping strategy in the cognitively loaded medical curriculum. Study II focused on medical students’ regulation of learning and their conceptions of the learning environment in an innovative medical course where traditional lectures were combined wth problem-based learning (PBL) group work. First-year medical and dental students (N = 153) completed a questionnaire assessing their regulation strategies of learning and views about the PBL group work. The results indicated that external regulation and self-regulation of the learning content were the most typical regulation strategies among the participants. In line with previous studies, self-regulation wasconnected with study success. Strictly organised PBL sessions were not considered as useful as lectures, although the students’ views of the teacher/tutor and the group were mainly positive. Therefore, developers of teaching methods are challenged to think of new solutions that facilitate reflection of one’s learning and that improve the development of self-regulation. In Study III, a person-centred approach to studying regulation strategies was employed, in contrast to the traditional variable-centred approach used in Study I and Study II. The aim of Study III was to identify different regulation strategy profiles among medical students (N = 162) across time and to examine to what extent these profiles predict study success in preclinical studies. Four regulation strategy profiles were identified, and connections with study success were found. Students with the lowest self-regulation and with an increasing lack of regulation performed worse than the other groups. As the person-centred approach enables us to individualise students with diverse regulation patterns, it could be used in supporting student learning and in facilitating the early diagnosis of learning difficulties. In Study IV, 91 student teachers participated in a pre-test/post-test design where they answered open-ended questions about a complex science concept both before and after reading either a traditional, expository science text or a refutational text that prompted the reader to change his/her beliefs according to scientific beliefs about the phenomenon. The student teachers completed a questionnaire concerning their regulation and processing strategies. The results showed that the students’ understanding improved after text reading intervention and that refutational text promoted understanding better than the traditional text. Additionally, regulation and processing strategies were found to be connected with understanding the science phenomenon. A weak trend showed that weaker learners would benefit more from the refutational text. It seems that learners with effective learning strategies are able to pick out the relevant content regardless of the text type, whereas weaker learners might benefit from refutational parts that contrast the most typical misconceptions with scientific views. The purpose of Study V was to use eye tracking to determine how third-year medical studets (n = 39) and internal medicine residents (n = 13) read and solve patient case texts. The results revealed differences between medical students and residents in processing patient case texts; compared to the students, the residents were more accurate in their diagnoses and processed the texts significantly faster and with a lower number of fixations. Different reading patterns were also found. The observed differences between medical students and residents in processing patient case texts could be used in medical education to model expert reasoning and to teach how a good medical text should be constructed. The main findings of the thesis indicate that even among very selected student populations, such as high-achieving medical students or student teachers, there seems to be a lot of variation in regulation strategies of learning and text processing. As these learning strategies are related to successful studying, students enter educational programmes with rather different chances of managing and achieving success. Further, the ways of engaging in learning seldom centre on a single strategy or approach; rather, students seem to combine several strategies to a certain degree. Sometimes, it can be a matter of perspective of which way of learning can be considered best; therefore, the reality of studying in higher education is often more complicated than the simplistic view of self-regulation as a good quality and external regulation as a harmful quality. The beginning of university studies may be stressful for many, as the gap between high school and university studies is huge and those strategies that were adequate during high school might not work as well in higher education. Therefore, it is important to map students’ learning strategies and to encourage them to engage in using high-quality learning strategies from the beginning. Instead of separate courses on learning skills, the integration of these skills into course contents should be considered. Furthermore, learning complex scientific phenomena could be facilitated by paying attention to high-quality learning materials and texts and other support from the learning environment also in the university. Eye tracking seems to have great potential in evaluating performance and growing diagnostic expertise in text processing, although more research using texts as stimulus is needed. Both medical and teacher education programmes and the professions themselves are challenging in terms of their multidisciplinary nature and increasing amounts of information and therefore require good lifelong learning skills during the study period and later in work life.

Organisational purchasing of service design – Agency and client perspectives

There has been an increase in the interest in service design, as companies have become more customer-centric and their focus has shifted to customer experiences. The actual organisational purchasing of service design has been given little attention, until recent years. The purpose of this study is to explore the purchasing of service design from the perspectives of sellers (service design agencies) and buying clients (business organisations). In order to understand the phenomenon, also agencies and clients’ approaches to service design discipline, purchasing processes, challenges related to purchasing and ways of facilitating the purchasing are explored. The research follows qualitative research method and utilises abductive reasoning. A proposition framework was formed by combining services marketing, design and organisational buying behaviour literatures, and was tested against real-life business cases. Empirical data was gathered by interviewing eight service design agency representatives and five client representatives in Finland. The results of semi-structural interviews were analysed by finding repetitive themes. The proposition framework was updated according to interview findings. There were both similarities and differences in service design agencies and clients’ approaches to service design. Service design represents a strategic activity to both parties, and it helps in clients’ business development and in discovering opportunities. It is an ideology; a way of thinking and working. The driving force for purchasing service design seemed to be something else than service design itself. Projects have been bought for 1) change and innovation related development, 2) channel related development or for 3) customer experience related development. Seven purchasing challenge themes were recognised: 1) poor or differing service design understanding, 2) selling of service design, 3) varying expectations, 4) difficulty of pre-evaluation, 5) buyers and buying companies, 6) project process and nature and 7) unclear project results. These all can be considered to cause challenges in organisational service design purchasing. Challenges can be caused by either participant, the agency or the client, and take place at any point of the purchasing process. Some of the challenges could be considered as barriers to purchasing or they play a role in an unsuccessful service project – and therefore, result in an unsuccessful organisational purchase. Purchasing could be facilitated in various ways by either participant; some ways are more attitude based, others actionable improvements. Thesis’s theoretical and managerial findings can be utilised to both improve the selling and purchasing of service design services.

Value-based selling of the column connection solution as part of project sales

The objective of this study was to find out how third party influencers can facilitate value-based selling in a network and how suppliers should aim to impact on these third party influencers to facilitate value-based selling. The study considers construction industry, selling the column connection solution and third party influencers. Third party influencers examined in this study were structural designers. The study also aims to find out structural designers’ value drivers and the differences between the market areas that this study related to. The theoretical part of the study focuses on two separate areas. The first part of the theory focuses on a value-based selling concept: what it is, what it requires and what are the main barriers for value-based selling. The second part of the theory examines value creation in networks. The present knowledge over value creation in networks and different network actors are presented. Project marketing is also discussed briefly because this study’s topic, which is highly related to project business. The results reveal structural designers’ value drivers considering the usage of the column connection solution and present ways how suppliers should aim to impact structural designers to facilitate value-based selling. The main result of the study indicates that third party influencers can have a positive impact on facilitating value-based selling. Structural designers are communicating more or less with all the salient actors in different project phases and they can act as sponsors to support the sales of Peikko’s column connection solution and promote solution to other actors involved to the project. This requires that structural designers can understand the actual benefits of how the solution can improve their and their customers’ business.

Online problem-based learning : perceptions of nursing educators /

A qualitative study was conducted to detennine 5 nursing educators' perceptions about the online application of a problem-based learning strategy in undergraduate nursing education. The question asked in the study was: Can the essential elements of face-to-face problem-based learning be supported in an online format? The data for this study came from 2 individual tape-recorded interviews with each of the 5 participants over a 3-month period and from a researchjournaI. The educators felt that student-centered learning and critical thinking could be supported within an online format. However, they noted that challenges could exist in terms of developing tutor roles, fostering student self-direction, facilitating group process and connections, and incorporating a nursing philosophy of online learning. The importance of tailoring an online problem-based learning course to reflect educators' philosophies and values in nursing emerged as an important theme from the interview responses. Overall, the participants suggested that an ideal environment would blend both face-to-face and online elements and that fewer elements would be offered in the first 2 years of the nursing program. They described a hybrid model of problem-based learning in which the online component could be used to support face-to-face sessions.

Bird depredation of grapes in Niagara vineyards : a novel approach to identifying spatial and temporal trends /

Although local grape growers view bird depredation as a significant economic issue, the most recent research on the problem in the Niagara Peninsula is three decades old. Peer-reviewed publications on the subject are rare, and researchers have struggled to develop bird-damage assessment techniques useful for facilitating management programmes. I used a variation of Stevenson and Virgo's (1971) visual estimation procedure to quantify spatial and temporal trends in bird damage to grapes within single vineyard plots at two locations near St. Catharines, Ontario. I present a novel approach to managing the rank-data from visual estimates, which is unprecedented in its sensitivity to spatial trends in bird damage. I also review its valid use in comparative statistical analysis. Spatial trends in 3 out of 4 study plots confirmed a priori predictions about localisation in bird damage based on optimal foraging from a central location (staging area). Damage to grape clusters was: (1) greater near the edges of vineyard plots and decreased with distance towards the center, (2) greater in areas adjacent to staging areas for birds, and (3) vertically stratified, with upper-tier clusters sustaining more damage than lower-tier clusters. From a management perspective, this predictive approach provides vineyard owners with the ability to identify the portions of plots likely to be most susceptible to bird damage, and thus the opportunity to focus deterrent measures in these areas. Other management considerations at Henry of Pelham were: (1) wind damage to ice-wine Riesling and Vidal was much higher than bird damage, (2) plastic netting with narrow mesh provided more effective protection agsiinst birds than nylon netting with wider mesh, and (3) no trends in relative susceptibility of varietals by colour (red vs green) were evident.

Female administrators and the mentors who give them full support /

A looming attrition rate, a steady increase in the number of women in administration, and a lack of Canadian research all provided the rationale for this study. The problem in this study was to investigate the needs and challenges of new female administrators and to examine the role that mentors play in addressing these issues. This study also explored the perceived benefits of having a mentor. This study examined the inductive year of 33 female administrators from 3 Ontario school boards. It was a qualitative and quantitative design, using questionnaire and interview data. It was found that the majority felt that they struggled with biases and expectations that were gender specific. The challenges that were perceived to be most prevalent were categorized into 4 thematic areas: Maintaining Balance, Feeling Pressured, The Perceptions of Others, and Being Challenged by Others. Regarding the benefits of mentoring, the participants perceived mentoring to be most beneficial in terms of professional growth, followed by learning how to run a school, and then career advancement. The significance of this study was threefold: it had theoretical implications as well as implications for practice and future research. Suggestions included: facilitating longitudinal relationships, having the board become more actively involved in facilitating the relationship, and implementing an internship program. This study attempted to extend the current literature by theorizing that a mentorship is cyclical in nature. Future research could include program design and implementation, as well as providing consistent and accessible mentoring opportunities for all.

Gaining a better understanding of how Outward Bound Western Canada course outcomes are achieved : a research study /

This study examined how Outward Bound Western Canada (OBWC) course outcomes are achieved by exploring the relationships among course components, students' characteristics, and course outcomes. OBWC is a wilderness-based adventure education organization that helps students achieve outcomes such as increased self-awareness, self-confidence, motivation, interpersonal skills, concern for others, and concern for the environment. This study explored the ways in which the various components of courses and the characteristics of students contribute to determining the outcomes students experience as a result of their courses. The purpose of the study was to gain a better understanding of how OBWC course outcomes are achieved in order to strengthen adventure education theory, enhance practice at OBWC and other adventure education organizations, and provide a foundation for further research on this topic. As an interpretive case study, this study sought to describe how OBWC course outcomes are achieved and to provide interpretations of the research findings. Data was gathered from OBWC students and instructors using the quantitative and qualitative data collection techniques of questionnaire, interview, and observation. Data collected from 98 participants ensured a considerable breadth to the study, while interviews with a number of participants also enabled the collection of in-depth data. Analysis and triangulation of the data from the various sources allowed discernment of the research findings. A comprehensive and detailed picture of how course outcomes are achieved emerged from the findings. Twenty-nine course components were found to influence course outcomes, including various aspects of course activities, the physical environment, instructors, and the group. The findings indicated that certain course components were most influential in determining increases to students' self-awareness, self-confidence, self-reliance, self-esteem, self-concept, motivation, self-responsibility, interpersonal skills, concern for others, and concern for the environment. A number of course components were found to indirectly contribute to positive course outcomes by helping maximize the effectiveness of other components, by increasing students' motivation while on course, or by facilitating the processing and transference of new information. The findings also suggested that several course components either directly or indirectly affected course outcomes in negative ways. In addition, the gender, age, population, and expectations of students were found to play a role in determining the course outcomes they experienced and in determining which course components caused those outcomes. Interpretation of the findings resulted in the generation of research-based theory. The main theoretical argument derived from the results of the study was that course outcomes are influenced by a combination of course components and characteristics of students. More specifically, the theory generated by the study indicated that five groupings of factors contribute to course outcomes, including course activities, the physical environment, instructors, the group, and students' characteristics. The study was considered in relation to existing adventure education literature and larger theoretical issues. The generated theory and research findings were then used to develop suggestions for improving practice at OBWC and other adventure education organizations, as well as for enhancing future research studies.

Teacher professional growth in an authentic learning environment

The last several decades have been marked by tremendous changes in education - technological, pedagogical, administrative, and social. These changes have led to considerable increments in the budgets devoted to professional development for teachers ~ with the express purpose of helping them accommodate their practices to the new realities oftheir classrooms. However, research has suggested that, in spite of the emphasis placed on encouraging sustained change in teaching practices, little has been accomplished. This begs the question of what ought to be done to not only reverse this outcome, but contribute to transformational change. The literature suggests some possibilities including: a) considering teachers as learners and applying what, is known about cognition and learning; b) modifying the location and nature ofprofessional development so that it is authentic, based in the classroom and focusing on tasks meaningful to the teacher; c) attending to the infrastructure underlying professional development; and d) ensuring opportunities for reflective practice. This dissertation looks at the impact of each ofthese variables through an analysis ofthe learning journeys of a group ofteachers engaged in a program called GrassRoots in one midsized school board in Ontario. Action research was conducted by the researcher in his role as consultant facilitating teacher professional growth around the use of Web sites as culminating performance tasks by students. Research focused on the pedagogical approach to the learning of the teachers involved and the infrastructure underlying their learning. Using grounded theory, a model for professional development was developed that can be used in the future to inform practices and, hopefully, lead to sustained transformational school change.

Displaced women professionals: an exploration of perceived learning processes during workplace transition /

This study focused on obtaining a deeper understanding of the perceived learning of female professionals during workplace transition. The women's lived experiences were explored through a feminist interpretive lens (Bloom, 1998). The study also drew upon concepts from adult learning such as barriers and facilitating factors to learning, resistance, transformative learning, and multiple ways of knowing. Five women participated in a 1 -hour interview and a focus group activity. The findings are presented under the 2 broad themes of perceived learning and factors affecting learning. The most common theme of perceived learning was participants' experience of increased self-knowledge. Additionally, while learning was thought of as a struggle, it provided either an opportunity for a reexamination of goals or a reexamination of self. Reflection by participants seemed to follow two orientations and other types of perceived learning included experiential, formal, and informal learning. In the broad theme of factors affecting learning, contradictions and conflict emerged through the examination of participants' multiple subjectivities, and within their naming of many factors as both facilitating factors and barriers to learning. The factors affecting learning themes included personal relationships, professional communities, selfesteem, attitude and emotion, the gendered experience of transition, time, and finances. The final theme explored participants' view of work and their orientations to the future. A proposed model of learning during workplace transition is presented (Figure 1 ) and the findings discussed within this proposed model's framework. Additional developmental theories of women (Josselson, 1987; Levinson & Levinson, 1996), communities of practice theories (Wenger, 1998), and career resilience theories (Pulley, 1995) are discussed within the context of the proposed model. Implications to practice for career counsellors, people going through workplace transition, human resource managers and career coaches were explored. Additionally implications to theory and future areas of research are also discussed.

Developing and nurturing professional learning communities: principles used by elementary administrators /

This study examined the strategies used by elementary school principals to facilitate and nurture the development of professional learning communities (PLC) within their school settings. Using a reputational sample of administrators whose schools were demonstrating observable characteristics of PLCs, this study documented and described the strategies and actions taken by the principals to move their schools forward. Data collection included the use of open-ended interviews as well as observations capturing the means by which the principals addressed the areas of culture, processes, and structures within their school setting. A grounded theory approach to data analysis uncovered 4 guiding principles used by the principals to facilitate the development of the PLCs within their school: (a) protecting the purpose; (b) attending to relationships; (c) sharing the responsibility; and (d) valuing the journey. The guiding principles were used by each administrator to anchor the decisions they made and develop responsive, contextspecific strategies to support the PLC at their school. The results highlighted the complex role of the principal and the supports required to tackle the difficult work of facilitating PLCs.