Ionic Liquids and Microwaves in Promotion of Organic Synthesis : Friedel-Crafts reaction, deuterolabelling and O-Demethylation

The use of ionic liquids in chemical research has gained considerable interest and activity in recent years. Due to their unique and varied physicochemical properties, in comparison to molecular solvents, the potential applications for ionic liquids are enormous. The use of microwave irradiation, as a powerful dielectric heating technique, in synthetic organic chemistry has been known since 1986. Since then, it has gained significant recognition for its research and application in both academia and industry. The use of either ionic liquids or microwave irradiation in synthetic organic chemistry has been known to afford improved, alternative or complimentary selectivities, in comparison to traditional processes. In this study, the use of ionic liquids as solvents, co-solvents and catalytic media was explored in Friedel-Crafts, deuterolabelling and O-demethylation reactions. Alternative methods for the production of a variety of aromatic ketones using the Friedel-Crafts acylation methodology were investigated using ionic liquid catalyst or ionic liquid acidic additive systems. The disclosed methods, i.e. metal bistriflamides and chloroindate ionic liquids systems, possessed good catalytic activity in the synthesis of typical benzophenones. These catalytic systems were also recyclable. Microwave irradiation was found to be useful in the synthesis of various polyhydroxydeoxybenzoins and arylpropanones as synthetic precursors to naturally occurring or potentially bioactive compounds. Under optimized condition, the reaction occurred in only four minutes using systems such as [bmim][NTf2]/HNTf2 and [bmim][BF4]/BF3·OEt2. Naturally occurring polyphenols, such as isoflavones, can possess various types of biological or pharmacological activity. In particular, some are noted for their beneficial effects on human health. Isotopically labelled analogues of polyphenols are valuable as analytical standards in the quantification of these compounds from biological matrices. A new strategy for deuterolabelling of polyphenols was developed using ionic liquids as co-solvents and 35% DCl/D2O, as a cheap deuterium source, under microwave irradiation. Under these conditions, perdeuterated compounds were achieved in short reaction times, in high isotopic purity and in excellent yields. An O-demethylation reaction was developed, using an ionic liquid reaction medium with BBr3 for the deprotection of a variety methyl protected polyphenolic compounds, such as isoflavons and lignans. This deprotection procedure was found to be very practical as the reaction occurred under mild reaction conditions and in short reaction times. The isolation and purification steps were particularly straightforward and high yielding, in comparison to traditional methods.

Moderneja ryijyjä, metritavaraa ja käsityötä : Tekstiilitaide ja nykyaikaistuva taideteollisuus Suomessa maailmansotien välisenä aikana

Modern ryijys, fabric by the yard and handicrafts. Finnish textile art and modernizing applied art during the inter-war years Textile art was in the 1920s and 1930s in the front rank of Finnish applied art and design. Modern ryijys, tapestries and fabrics by the yard by contemporary textile artists were on show in Finland and abroad. Textile art had also become interesting commercially, especially in interior textiles of modern homes. The research uses sources of the Ornamo Association of Decorative Artists, for example the Ornamo year books published from 1927, the Finnish Society of Crafts and Design and the country s only school of applied arts, the Central School of Arts and Crafts and the Museum of Applied Arts maintained by the society and also the national specialist organisation the Friends of Finnish Handicraft. It also refers to the magazines Käsiteollisuus and Kotiliesi. The art historical dissertation studies the renaissance of weaving art of the inter-war years in Finland. It problematizes the relation of the succesfull and appreciated textile art to the concept of breakthrough of Modernism (Functionalism). With the material from textile artists activities it questions the prevailing idea of slow modernization of Finnish applied art and design and challenges the polarization of craft and industry in the discourses of Modernisms of design. The public discussions about modernization of design and applied art where textile art and especially the ryijy got sometimes into difficult positions are interpreted as power struggles. After taking independence in 1917 the Finnish tradition of ryijy rugs was set as a symbol of the original culture of the young nation. The research studies the development of the so called art ryijy and the notions and meanings of hand weaving in the national context and also in relation to contemporary events in international applied art and design. It highlights the continuity of hand crafted production of textiles and the strong position of textile artists working in this field. The research opens new perspectives to Finnish textile artists by showing their activities as entrepreneurs in their own weaving studios or design studios and referring to their many relations and functions as pattern designers and educators in the growing handicraft industries.

Yhteinen käsityö peruskoulun 7. luokalla : Opettajien kokemuksia yhteisen käsityön opetuksesta ja organisoinnista

Finnish education politics presume that basic education should be equal to all students. While organising craft education equality can be understood as similarity or as possibility to choose. The possibility to be able to choose whether textile or technical craft despite of one´s gender has been the aim of laws and curriculums already over 30 years. In practice it´s almost impossible to students to ignore feminine and masculine roles that go deep into our culture. Choosing craft has been divided by gender, which is the reason why possibility to choose has not been good enough to educationalists of equality. The latest guidelines for the National core curriculum for bacis education were issued in 2004. According to curriculum craft education consists parts of both technical and textile craft. All students should take part in both sectors of crafts. Furthermore, one can be given a possibility to consentrate his studies in whether textile or technical craft. The curriculum does not set the rules how the education should be organised, which means that it can be organised in many ways depending on city, school or teacher. Teachers and other specialists have contradictory feelings towards shared craft education, because traditional way to see craft in Finland is to separate textile craft from technical craft. Both crafts have some common features that are introduced in curriculum. Besides there is many equal things in craft theories that bind textile and technical craft to each other. The main purpose of this research was to find out, how shared craft education has been organised at the 7.th grade in Finnish comprehensive school, and which things affect in the settlements. Second goal was to describe and compare teachers´ experiences in teaching shared craft education. Third aim of this study was how shared craft has changed craft education. I collected the research material in May 2006 by interviewing both textile and technical craft teachers who teach shared craft. The material consists of fourteen theme interviews. In the analysis of the material I used theoretic bounded document analysis. According to the research there are three different ways to organise shared craft education: 50 50-arrangement, exchanging period and project week. In the schools that carried out 50 50-arrangement teaching was realised mainly in heterogenous groups. Principals had usual a lot of authorization on how to arrange craft education, which means that their views on equality, laws and curriculum affected in the settlemets more than teachers´ opinions. Teachers´ attitudes to shared craft were mainly positive. The changing of craft education can be divided in two parts: the aims and the containings of the curriculum have changed, as well as the meaning of the craft as core subject. Teachers have been forced to decrease the containings of both textile and technical crafts. Despite of eliminations both crafts still have comprehensive containings. Teachers decided what to teach by these argumets: Students should learn some basic things or produce a certain product. Usually teachers had also a lot of experience and special intrests in crafts. According to this research there is four significant meanings for shared craft education: 1) developing readiness for doing things, 2) developing skills of thinking, 3) delight of doing things and 4) teaching attitude.

Käsityön sukupuolirajat ja rajojen rikkojat

Gender-specific division of crafts is significant in Finnish culture. The aim of craft education in comprehensive schools has been to unify education for both girls and boys during the thirty years of modern comprehensive education, but in reality crafts has diverged into two different subjects for girls and boys. Craft education has taught different things: girls have been taught things that are feminine and included in private life, while the boys’ education has been mostly directed at public and working life. At the same time girls and boys have been educated and socialized towards a certain womanhood and manhood. Craft as a hobby is also very gender divided but there are some clues that tell of the changing positions on the border areas. The starting point of this study has been the assumption that gender structures within crafts can be transformed. But it is important to know the background that creates and maintains these constructions and the expedients for dismantling the structures. The main purpose of this study is to find out how the gender-specific crafts are changing and how they are still maintained. My study analyses why men and woman have chosen untypical hobbies and through that I shall discuss how gendered structures can be dismantled. In the autumn of 2008 I interviewed borderline breakers within crafts: men who had an interest in textile crafts and women who had an interest in technical work. Informants of this study were 20-31 years old and they studied behavioural sciences. The data was collected in 12 theme interviews and document analysis was used to study the results. The dismantling of the gender divide in crafts is slow, but new borders are drawn all the time. The informants have started textile and technical handicrafts soon after comprehensive school or during their studies at university. A main motivation for the new hobby has been the possibility to study for a teacher’s degree with technology or textile studies as a main or a secondary subject. Gender-specific division of crafts is constructed early in childhood as different skills are taught to girls and boys. School teaches gender specific skills and the different skills of girls and boys have not been taken into account. Instead, it has been assumed through comprehensive school that both girls and boys share certain basic skills, and attention has not been paid to the differences between genders. At university the same assumption has still thrived. Skill levels between men and women are substantial and that may have hindered a move by women to technical studies and by men to textile studies. Hence an assumption of naturally gendered crafts has been developed.

Käsityökohtaamisia muinaisuuden kanssa : Neulalla neulominen eli kinnasneulatekniikka ...muutakin kuin neulakinnas?

The aim of this study was to find out how the technique of knotless netting is perceived by the craftsperson of the twenty first century. In this study the craftspeople are represented by the researcher herself, seven craftspeople and teachers (3) teaching knotless netting as well as their students (21). The main interests of this study are the mental pictures and relationship to knotless netting that craftspeople have in the twenty first century. Points of focus are also the specific characteristics of knotless netting, as well as experimenting with new and different materials. The aim of these experiments has been to find new and unusual uses for knotless netting. Preserving knotless netting as a craft and technique are also questions dealt with in this study. The methodology of this study is a qualitative and phenomenographic study of several cases. The data collected are interviews of the teachers, observations in two knotless netting courses, questionnaires answered by the students in these courses and experimental samples made by the author and evaluated by other craftspeople. These samples were made during the years 2005-2008. The interviews, questionnaires and evaluations were conducted under winter and spring 2008. The reference literature is comprised from publications in several different fields. In this study ethnography is the most dominant field of reference due to the fact that knotless netting is so strongly linked to history and antiquity. In the past the technique of knotless netting has been passed down from generation to generation in whatever form the teacher has known. There are many different ways of stitching and binding in knotless netting. This technique is closely connected to traditional knotless netting mittens even today. Nowadays knotless knitting is taught in craft schools, evening classes and in other recreational courses. The concrete understanding of knotless netting by means of two-dimensional instructions is challenging. Craftspeople often require somebody to actually demonstrate the correct way to make the stitches and hold the work before they can proceed with the technique. The way knotless netting is perceived by craftspeople is linked to their backgrounds and preconstructed mental images concerning the technique. An etnographer approaches knotless netting in a different way from a crafts-scientist or a person in an evening class wishing to master the technique. The attitude of the teacher is passed on to students and also affects the way the student perceives knotless netting and its possibilities as a technique. A craftsperson has mixed feelings toward knotted netting. On the other hand the surfaces produced by this rare technique are intriguing but the costs due to the slow manufacturing process are seen as an encumbrance.

Käsityötä, kotiteollisuutta ja sosiaalihuoltoa : Työtupa Aunuksessa 1941-1944

When Finland occupied East Karelian territories in Soviet Union during The Continuation War (1941 1944) Finnish people had also to take care of the inhabitants of the occupied East Karelia. For example there was a lack of clothes and shoes during the wartime. In order to facilitate clothing situation and to provide more opportunities to work for women, Finnish people founded some workshops in East Karelia. Workshops also helped to collect East Karelian craft products. One of the workshops was founded in the city of Olonets in October 1941 and it was in operation until June 1944. This workshop is the subject of this thesis. The aim of this thesis is to find out with the microhistorical approach what kind of functions the workshop of Olonets had during The Continuation War and who worked in the workshop. In this thesis I also examine women s crafts in the Olonets workshop and their meaning during the wartime. I collected the material of this thesis from different places. In February 2010 I interviewed Talvikki Lausala, the leader of the Olonets workshop, who worked in the Olonets from May 1942 to June 1944. From the Virkki Käsityömuseo I looked for objects which have been made in the workshop of Olonets. Tyyne-Kerttu Virkki collected crafts from the East Karelia when she was working in the area and in the workshop from 1941 to 1944. Archive material I found from the Finnish National archive and from the archive of the Tyyne-Kerttu Virkki -Foundation. East Karelian women and girls who were not able to do anything else came to work in the Olonets workshop. If women could not go to work outside of home, they had an option to do the same crafts at home. There were three Finnish women, Tyyne-Kerttu Virkki, Talvikki Lausala and Sofi Nyrkkö, who worked and led in the workshop of Olonets. In addition to the workshop, there was a dress maker s atelier in which clothes were made to order and soldiers uniforms were repaired, a small museum and a shop to sell products of the workshop. Craft products were also exported to Finland. Courses were organized in which Finnish women taught East Karelian crafts.

Näppärien mummojen muistelukirjonta - yhteisöllistä ja voimauttavaa käsityöilmaisua

The aim of the study was to get acquainted with the activity of Näppärät Mummot, a Lahti-based crafts society, and its importance to the wellness of the members of the group. The selected aim, i.e., analyzing the wellness, largely affected the whole research process and its results. According to earlier studies in the field, different forms of craft and expressional activity promote one's wellness as well as support the work for one's identity. Based on my theoretical knowledge, my research was set out to: 1) form a general view of crafts culture within Näppärät Mummot and 2) find out how recollective craft that promotes wellness is perceived through communality, experiential activity, work for one's identity, and divided as well as undivided craft. Qualitative field work was governed by ethnographic research strategy, according to which I set out to get thoroughly familiar with the society I was studying. The methods I used to collect data were participant observation and thematic interview. I used a field diary for writing down all data I acquired through the observation. The interviewee group was formed by seven members of Näppärät Mummot. An mp3 recorder was used to record the interviews, which I transcribed later. The method for data analysis was qualitative content analysis, for which I used Weft QDA, a qualitative analysis software application. I formed themes that shed light on research tasks from the data using coding and theory-driven analysis. I kept literature and data I collected in cooperation through the whole analysis process. Lastly, drawing from the classes of meaning of therapeutic craft that I sketched by means of summarizing and classifying, I presented the central concepts that describe the main results of the study. The main results were six concepts that describe Näppärät Mummot's crafts culture and recollective craft with its wellness-beneficial effect: 1) autobiographical craft, 2) shared work for one's identity, 3) shared intention for craft, 4) craft as a partner, 5) individual manner of craft, and 6) shared improvement. Craft promoted wellness in many ways. It was used to promote inner life management in difficult times and it also provided sensations of empowerment through pleasure from craft. Expressional, shared craft also served as means of reinforcing one's identity in various ways. Expressional work for one's identity through autobiographical themes of craft represented rearranging one's life through holistic craft. A personal way of doing things also served as expressional action and work for one's identity even with divided craft. Shared work for identities meant reinforcing the identities of the members through discources of craft and interaction with their close ones. What proves the interconnection between communality and craft as well as their shared meaning is that communality motivated the members to work on their craft projects, while craft served as the means of communication between the members: communication through craft was easier than lingual communication. The results can not be generalized to apply to other groups: they are used to describe the versatile means of recollective craft to promote the well-being among the crafts society Näppärät Mummot. However, the results do introduce a new perspective to the social discussion on how cultural activities promote well-being.

Leisure activities and obesity in adolescence : a follow-up study among twins

The aims of this dissertation were 1) to investigate associations of weight status of adolescents with leisure activities, and computer and cell phone use, and 2) to investigate environmental and genetic influences on body mass index (BMI) during adolescence. Finnish twins born in 1983–1987 responded to postal questionnaires at the ages of 11-12 (5184 participants), 14 (4643 participants), and 17 years (4168 participants). Information was obtained on weight and height, leisure activities including television viewing, video viewing, computer games, listening to music, board games, musical instrument playing, reading, arts, crafts, socializing, clubs, sports, and outdoor activities, as well as computer and cell phone use. Activity patterns were studied using latent class analysis. The relationship between leisure activities and weight status was investigated using logistic and linear regression. Genetic and environmental effects on BMI were studied using twin modeling. Of individual leisure activities, sports were associated with decreased overweight risk among boys in both cross-sectional and longitudinal analyses, but among girls only cross-sectionally. Many sedentary leisure activities, such as video viewing (boys/girls), arts (boys), listening to music (boys), crafts (girls), and board games (girls), had positive associations with being overweight. Computer use was associated with a higher prevalence of overweight in cross-sectional analyses. However, musical instrument playing, commonly considered as a sedentary activity, was associated with a decreased overweight risk among boys. Four patterns of leisure activities were found: ‘Active and sociable’, ‘Active but less sociable’, ‘Passive but sociable’, and ‘Passive and solitary’. The prevalence of overweight was generally highest among the ‘Passive and solitary’ adolescents. Overall, leisure activity patterns did not predict overweight risk later in adolescence. An exception were 14-year-old ‘Passive and solitary’ girls who had the greatest risk of becoming overweight by 17 years of age. Heritability of BMI was high (0.58-0.83). Common environmental factors shared by family-members affected the BMI at 11-12 and 14 years but their effect had disappeared by 17 years of age. Additive genetic factors explained 90-96% of the BMI stability across adolescence. Genetic correlations across adolescence were high, which suggests similar genetic effects on BMI throughout adolescence, while unique environmental effects on BMI appeared to vary. These findings suggest that family-based interventions hold promise for obesity prevention into early and middle adolescence, but that later in adolescence obesity prevention should focus on individuals. A useful target could be adolescents' leisure time, and our findings highlight the importance of versatility in leisure activities.

Hantavirus infection: Insights into entry, assembly and pathogenesis

Hantaviruses (family Bunyaviridae, genus Hantavirus) are enveloped viruses incorporating a segmented, negative-sense RNA genome. Each hantavirus is carried by its specific host, either a rodent or an insectivore (shrew), in which the infection is asymptomatic and persistent. In humans, hantaviruses cause Hemorrhagic fever with renal syndrome (HFRS) in Eurasia and Hantavirus cardiopulmonary syndrome (HCPS) in the Americas. In Finland, Puumala virus (genus Hantavirus) is the causative agent of NE, a mild form of HFRS. The HFRS-type diseases are often associated with renal failure and proteinuria that might be mechanistically explained by infected kidney tubular cell degeneration in patients. Previously, it has been shown that non-pathogenic hantavirus, Tula virus (TULV), could cause programmed cell death, apoptosis, in cell cultures. This suggested that the infected kidney tubular degeneration could be caused directly by virus replication. In the first paper of this thesis the molecular mechanisms involved in TULV-induced apoptosis was further elucidated. A virus replication-dependent down-regulation of ERK1/2, concomitantly with the induced apoptosis, was identified. In addition, this phenomenon was not restricted to TULV or to non-pathogenic hantaviruses in general since also a pathogenic hantavirus, Seoul virus, could inhibit ERK1/2 activity. Hantaviruses consist of membrane-spanning glycoproteins Gn and Gc, RNA-dependent RNA polymerase (L protein) and nucleocapsid protein N, which encapsidates the viral genome, and thus forms the ribonucleoprotein (RNP). Interaction between the cytoplasmic tails of viral glycoproteins and RNP is assumed to be the only means how viral genetic material is incorporated into infectious virions. In the second paper of this thesis, it was shown by immunoprecipitation that viral glycoproteins and RNP interact in the purified virions. It was further shown that peptides derived from the cytoplasmic tails (CTs) of both Gn and Gc could bind RNP and recombinant N protein. In the fourth paper the cytoplamic tail of Gn but not Gc was shown to interact with genomic RNA. This interaction was probably rather unspecific since binding of Gn-CT with unrelated RNA and even single-stranded DNA were also observed. However, since the RNP consists of both N protein and N protein-encapsidated genomic RNA, it is possible that the viral genome plays a role in packaging of RNPs into virions. On the other hand, the nucleic acid-binding activity of Gn may have importance in the synthesis of viral RNA. Binding sites of Gn-CT with N protein or nucleic acids were also determined by peptide arrays, and they were largely found to overlap. The Gn-CT of hantaviruses contain a conserved zinc finger (ZF) domain with an unknown function. Some viruses need ZFs in entry or post-entry steps of the viral life cycle. Cysteine residues are required for the folding of ZFs by coordinating zinc-ions, and alkylation of these residues can affect virus infectivity. In the third paper, it was shown that purified hantavirions could be inactivated by treatment with cysteine-alkylating reagents, especially N-ethyl maleimide. However, the effect could not be pin-pointed to the ZF of Gn-CT since also other viral proteins reacted with maleimides, and it was, therefore, impossible to exclude the possibility that other cysteines besides those that were essential in the formation of ZF are required for hantavirus infectivity.

Löydöstä muinaispuvuksi : arkeologisten tekstiilien ennallistaminen

From a find to an ancient costume - reconstruction of archaeological textiles Costume tells who we are. It warms and protects us, but also tells about our identity: gender, age, family, social group, work, religion and ethnicity. Textile fabrication, use and trade have been an important part of human civilization for more than 10 000 years. There are plenty of archaeological textile findings, but they are small, fragmentary and their interpretation requires special skills. Finnish textile findings from the younger Iron Age have already been studied for more than hundred years. They have also been used as a base for several reconstructions called muinaispuku , ancient costume. Thesis surveys the ancient costume reconstruction done in Finland and discusses the objectives of the reconstruction projects. The earlier reconstruction projects are seen as a part of the national project of constructing a glorious past for Finnish nationality, and the part women took in this project. Many earlier reconstructions are designed to be festive costumes for wealthy ladies. In the 1980s and 1990s many new ancient costume reconstructions were made, differing from their predecessors at the pattern of the skirt. They were also done following the principles of making a scientific reconstruction more closely. At the same time historical re-enactment and living history as a hobby have raised in popularity, and the use of ancient costumes is widening from festive occasions to re-enactment purposes. A hypothesis of the textile craft methods used in younger Iron Age Finland is introduced. Archaeological findings from Finland and neighboring countries, ethnological knowledge of textile crafts and experimental archaeology have been used as a basis for this proposition. The yarn was spinned with a spindle, the fabrics woven on a warp-weighted loom and dyed with natural colors. Bronze spiral applications and complicated tablet-woven bands have possibly been done by specialist craftswomen or -men. The knowledge of the techniques and results of experimenting and experimental archaeology gives a possibility to review the success of existing ancient costume reconstructions as scientific reconstructions. Only one costume reconstruction project, the Kaarina costume fabricated in Kurala Kylämäki museum, has been done using as authentic methods as possible. The use of ancient craft methods is time-consuming and expensive. This fact can be seen as one research result itself for it demonstrates how valuable the ancient textiles have been also in their time of use. In the costume reconstruction work, the skill of a craftswoman and her knowledge of ancient working methods is strongly underlined. Textile research is seen as a process, where examination of original textiles and reconstruction experiments discuss with each other. Reconstruction projects can give a lot both to the research of Finnish younger Iron Age and the popularization of archaeological knowledge. The reconstruction is never finished, and also the earlier reconstructions should be reviewed in the light of new findings.