Romanianunkarilaisuuden ja udmurttilaisuuden representaatio sanomalehtiteksteissä : Lähestymistapoja kielen ja identiteetin suhteen tarkasteluun sosiolingvististä taustaa vasten

Tutkielman tavoitteena on testata ja arvioida tekstianalyysin menetelmien toimivuutta vähemmistökielen puhujien identiteetin tutkimisessa sekä selvittää udmurttien ja Transilvanian unkarilaisten vähemmistöidentiteetin erikois-piirteitä. Työssäni tarkastelen etnonyymien magyar 'unkarilainen' ja udmurt 'udmurtti' esiintymistä lehtiteksteissä. Aineistoni koostuu Romanian unkarilaisvähemmistön sekä udmurttivähemmistön omakielisissä sanomalehdissä alkuvuodesta 2007 ilmestyneistä lehtiteksteistä. Unkarilaisesta Szabadság-lehdestä valitsin tarkasteluun 79 tekstiä, udmurtinkielisestä Udmurt duńńe -lehdestä 64. Tarkastelen etnonyymien magyar ja udmurt esiintymistiheyttä sekä sitä, millaisia pääsanoja ne määrittävät. Näiden tulosten avulla päättelen, kuinka keskeinen rooli näissä lehdissä on vähemmistön itseidentifioinnilla, ja pyrin selvittämään, esiintyykö lehdissä selviä vähemmistöidentiteetin rakennusstrategioita. Tilastollisen ja pääsana-analyysin täydennyksenä käytän kriittistä lähilukua: miten unkarilaiset ja udmurtit esitetään, millaisiksi heidät kuvataan ja miten esitetään heidän suhteensa valtaväestöön? Analyysi osoittaa, että Udmurt duńńe -lehdessä etnonyymi udmurt esiintyy 42 prosentissa teksteistä. Unkarilaisessa lehdessä sana magyar esiintyy vain 19 prosentissa teksteistä. Valtaosa udmurt-sanan esiintymistä on tapauksia, joissa se määrittää pääsanaa 'kieli'. Udmurtin kielen kehityksestä kirjoitetaan Udmurt duńńessa paljon ja uutisointi on sävyltään hyvin positiivista. Lehti antaa myönteisen mielikuvan udmurtin kielen nykytilasta ja tulevaisuudesta sekä eri kielten ja kansallisuuksien suhteista. Samanlaista ilmiötä ei ole havaittavissa Szabadságissa. Unkarin kieli mainitaan harvoin, ja näissä harvoissa tapauksissa aiheena ovat kieleen liittyvät ongelmat, esimerkiksi omakielisen opetuksen vaikeudet. Kansallisuuksien suhteita kuvataan enimmäkseen neutraalisti. Udmurt duńńesta puuttuu kielellisiä oikeuksia koskeva kritiikki lähes kokonaan. Eroja voidaan selittää sosiolingvistisen taustatiedon avulla. Asenteissa heijastuu vähemmistöjen erilainen historia. Udmurtin kieltä ei ole koskaan käytetty laaja-alaisesti modernissa yhteiskunnassa, kun taas unkarin kieli oli Transilvaniassa valtakieli aina ensimmäiseen maailmansotaan saakka. Unkarilaiset kokivat dramaattisen siirtymän vähemmistöasemaan, mutta oletettavasti muisto kielen vanhasta asemasta, tietoisuus sen täydestä käyttökelpoisuudesta yhteiskunnassa saa nykyisen vähemmistön edustajat valvomaan oikeuksiaan. Asiaan vaikuttanee myös Unkarin valtion läheisyys. Rajan takana on malli siitä, kuinka unkarin kieltä voidaan käyttää kaikilla elämänalueilla. Udmurteilla ei vastaavaa mallia ole, ja udmurtin kieli on jäänyt kotikielen asemaan. Oletettavasti Udmurt duńńen asennekampanja pyrkii nostamaan udmurtin kielen hupenevaa arvostusta. Romanian unkarilaisten keskuudessa unkarin kielen arvostus on ollut vankkaa, minkä vuoksi kieltä ei ole tarpeen pitää jatkuvasti esillä. Itsenäinen emämaa ja yli kymmenmiljoonainen puhujamäärä vakuuttavat osaltaan unkarin puhujat kielensä elinkelpoisuudesta. Voidaan todeta, että tekstien perusteella udmurttius usein pelkistyy udmurtin kielen taitoon ja käyttöön, kun taas unkarilaisuus ilmenee useilla eri elämänalueilla. Käyttämäni tilastollinen analyysi antaa karkean kuvan aiheen keskeisyydestä teksteissä, mutta todella luotettavan ja yleistettävän tiedon hankkimiseksi olisi käytettävä laajempaa korpusta. Myös useiden eri lehtien vertailu olisi hedelmällistä. Tarkimpia tuloksia antaa lähiluenta. Sen ongelmana on analysoitavan aineiston rajallisuus. Eräs ratkaisu ongelmaan on valitsemani pääsana-analyysi, mutta on huomattava, että myös sen tuloksien tulkitsemisessa lähiluenta on useimmiten tarpeen. Sosiolingvistinen taustatieto on välttämätöntä, jotta analyysin tuloksen saadaan sijoitettua oikeaan kontekstiin ja selitettyä.

Teori, praktik och yrkesval : En etnografisk analys av yrkeslivsrelevansen på Nordicas översättarlinje

Pro gradu -tutkielma “Teori, praktik och yrkesval: En etnografisk analys av yrkeslivsrelevansen på Nordicas översättarlinje” käsittelee pohjoismaisten kielten ja pohjoismaisen kirjallisuuden laitoksen (Nordican) kääntäjälinjan koulutusta. Tutkielman tavoite on tuottaa käytännöllistä tietoa kääntäjäkoulutuksen opinnoista ja opiskelijoista. Tietoa voidaan käyttää suunnitteluapuna Helsingin yliopiston kääntäjäkoulutuksen uudelleenorganisoinnissa, joka tapahtuu vuonna 2009. Tutkimuskysymyksissä keskitytään erityisesti Nordican kääntäjäkoulutuksen työelämäorientaatioon liittyviin opintoihin. Työelämäorientaation osuutta opinnoissa ja kääntäjälinjan opiskelijoiden opintosuunnittelua tutkitaan kyselytutkimuksen ja haastattelujen avulla. Kyselytutkimukseen on vastannut 19 nykyistä ja valmistunutta opiskelijaa kääntäjälinjalta (vastausprosentti on n. 36). Haastatteluihin on osallistunut viisi henkilöä – kolme opiskelijaa ja kaksi valmistunutta. Materiaalin suurin ongelma on aineiston vähyys ja se, että haastateltavista suurin osa opiskelee tai on opiskellut toisen kotimaisen kielen linjalla. Tutkimuksessa ei siis saada riittävästi tietoa äidinkielen linjan opiskelijoiden tilanteesta. Tutkimusmetodi on kvalitatiivinen osaksi aineiston pienuuden takia, mutta kyselytutkimuksen tuloksia analysoidaan myös kvantitatiivisesti. Kyselyn ja haastattelujen avoimet vastaukset analysoidaan etnografisen metodin avulla, joka soveltuu hyvin pienen aineiston analysointiin. Metodissa korostuvat tutkimuksen prosessiluonteisuus ja esimerkiksi tutkimuskysymysten muotoiluun ja materiaalin keräämiseen liittyvä joustavuus. Tutkimusmateriaalin analyysissa korostuu tutkimuskohteen kuvailun sijaan tulkinta. Tutkielman teoriaosuus käsittelee sekä kääntäjäkoulutuksen historiaa että nykyistä yliopistopedagogiikkaa. Johdannossa käsitellään myös Helsingin yliopiston työllistymiskartoituksia ja aikaisempia tutkimuksia Nordican ja käännöstieteen laitoksen opiskelijoiden sijoittumisesta työmarkkinoille. Teoreettisen viitekehyksen keskeisimmät aiheet ovat funktionaalinen kääntäjäkoulutus, kääntäjän kompetenssit, asiantuntijuus ja ammattimaisuus sekä teorian ja käytännön osuus opinnoissa. Teoriaosuus pohjustaa analyysin keskeisiä teemoja. Tutkimustulosten perusteella voi kumota osan tutkielman alussa esitetyistä hypoteeseista. Esimerkiksi kääntäjälinjan opiskelijoiden opintosuunnittelu ja halu suorittaa opintonsa yksinomaan kääntäjälinjalla ovat osoittautuneet oletettua johdonmukaisemmiksi. Opiskelijat ovat motivoituneita ja sitoutuvat kääntäjälinjan opintoihin muun muassa valitsemalla sivuaineita, jotka tukevat pääaineopintoja. Työelämäorientaation osalta tämänhetkiset opiskelijat vaikuttavat tyytyväisemmiltä opintoihinsa kuin jo valmistuneet kääntäjälinjalaiset. Haastateltavien yleinen käsitys on, että työelämäorientaatiota, ja erityisesti kääntäjän ammattiin liittyviä käytännön kysymyksiä, käsitellään opinnoissa liian vähän. Tutkielman tarkoitus on kartoittaa kääntäjälinjan opiskelijoiden ja valmistuneiden kääntäjälinjalaisten käsityksiä opintojen yhteydestä työelämään. Tutkimustulosten perusteella voidaan todeta, että akateemisiin opintoihin pitäisi sisältyä enemmän työelämäkontakteja. Työharjoittelu on ollut monelle tutkimuksen haastateltavalle hyvä kokemus, joka on johtanut harjoittelujakson jälkeiseen työsuhteeseen. Nordican uutta kääntäjäkoulutusta suunniteltaessa tulisikin ottaa huomioon työharjoittelun tärkeys. Monet haastateltujen mainitsemista koulutuksen kehittämiskohteista liittyvät resurssikysymyksiin. Kääntäjäkoulutuksen uudistuksen myötä voidaan toivottavasti vaikuttaa esimerkiksi erityisalojen kurssitarjontaan.

Om naturens förvandlingar : Vetenskap, kunskap och frihet i Rudolf Steiners tidiga tänkande. Idéhistoriska perspektiv på Waldorfpedagogiken

TRANSFORMATIONS OF NATURE Science, Knowledge and Freedom in the Early Thinking of Rudolf Steiner. Perspectives on Waldorf Education in the light of the History of Ideas Waldorf Education is based on the worldview that Rudolf Steiner (1861-1925) developed to a wide-ranging anthroposophical movement in the first decades of the 20th century. This thesis takes as its departure the early thinking of Rudolf Steiner that precedes anthroposophy, and its main purpose is to uncover the tradition of ideas represented in Steiner´s early life and which, in different ways, have emerged in the practice of Waldorf Education. Through systematic analysis I attempt to bring to light different aspects of Steiner’s early thinking: his concept of science, his epistemological startingpoints and his philosophy of freedom. By departing from J. W. Goethe’s qualitative concept of science, Steiner strove in his early works to formulate a monistic worldview which appears to be closely related to the Romantic Movement and its philosophy of nature. Characteristic traits of his thinking are, on the one hand, a critique of a one-sided enlightenment and, on the other hand, an aspiration to see the world as a living organic unity. Human beings can, by developing our intuitive faculties, get a deeper understanding of the indissoluble relationship between man and nature. Against this background Steiner´s early thinking can be read as a special kind of romantic development narrative. Steiner’s early thinking also opens the way for romantic perspectives on Waldorf Education. It appears that many central aims and conceptions in Waldorf Education can be illuminated by the epistemological perspective upon which Steiner elaborated early in his life. An organic curriculum, phenomenological didactics and high ideal of freedom can be considered seen as educational applications of conceptions that played an important role in Goethe and his age. Thus, Waldorf Education provides in our contemporary society an exceptional set of educational values: a holistic education with romantic undertones.

Kaveriporukasta liiketoiminnaksi : Tuotannon häiriöt ja organisaation oppiminen nopeasti muuttuvassa yrityksessä

In the 1990 s the companies utilizing and producing new information technology, especially so-called new media, were also expected to be forerunners in new forms of work and organization. Researchers anticipated that new, more creative forms of work and the changing content of working life were about to replace old industrial and standardized ways of working. However, research on actual companies in the IT sector revealed a situation where only minor changes to existing organizational forms were seen .Many of the independent companies faced great difficulties trying to survive the rapid changes in the products and production forms in the emerging field. Most of the research on the new media field has been conducted as surveys, and an understanding of the actual everyday work process has remained thin. My research is a longitudinal study of the early phases of one new media company in Finland. The study is an analysis of the challenges the company faced in a rapidly changing business field and the attempts to overcome these challenges. The two main analyses in the study focus on the developmental phases of the company and the disturbances in the production process. Based on these analyses, I study changes and learning at work using the methodological framework of developmental work research. Developmental work research is a Finnish variant of the cultural-historical activity theory applied to the study of learning and transformations at work. The data was gathered over a three-year period of ethnographic fieldwork. I documented the production processes and everyday life in the company as a participant observer. I interviewed key persons, video and audio-taped meetings, followed e-mail correspondence and collected various documents, such as agreements and memos. I developed a systematic method for analyzing the disturbances in the production process by combining the various data sources. The systematic analysis of the disturbances depicted a very complex and only partly managed production process. The production process had a long duration, and no single actor had an understanding of it as a whole. Most of the disturbances had to do with the customer relationships. The nature of the disturbances was latent; they were recognized but not addressed. In the particular production processes that I analyzed, the ending life span of a particular product, a CD-ROM, became obvious. This finding can be interpreted in relation to the developmental phase of the production and the transformation of the field as a whole. Based on the analysis of the developmental phases and the disturbances, I formulate a hypothesis of the contradictions and developmental potentials of the activity studied. The conclusions of the study challenge the existing understanding of how to conceptualize and study organizational learning in production work. Most theories of organizational learning do not address qualitative changes in production nor historical challenges of organizational learning itself. My study opens up a new horizon in understanding organizational learning in a rapidly changing field where a learning culture based on craft or mass production work is insufficient. There is a need for anticipatory and proactive organizational learning. Proactive learning is needed to anticipate the changes in production type, and the life cycles of products.

Onko varhaisen tuen päiväkoti mahdollinen? : Tutkimus varhaiskasvatuksen yhteisöllisestä kehittämisestä

Is the early childhood day care facility possible? The research considering communal development of the early education. In Finland mothers and fathers look after 400 000 pre-school children. Half of these attend day care facilities, in which 50 000 staff are employed. The aim of this research is to develop co-operation practices within the day care centre. This research refines and expands my own interest in and knowledge of day care management and content development. The basis of the research draws upon ethnographic material covering the period 1999–2005. The day care centre chosen as a central informant was the first suburban centre founded in 1963, and it provided a rich local and welfare state research perspective. It became clear that the day care facility’s co-operation practices formed the basis of bringing up children and at the same time produced a new multi-operational and multi-layered community for child participation. Adult day care centre workers bringing up the children as a professional work and solutions defining the conditions for the work are expressed in a child’s upbringing. This obviously has an impact in where as the development of communities. From the human and community scientific point of view, the group of youngest children will take up a future position as key players in communities as essential actors and reformers. The research was carried out as multiphase and multiscientific practical research and iterative data formation. The results verified that the co-operation between parents and day care staff produces important benefits for all the stakeholders. However, the day care staff has difficulties in implementing the benefits. During the research process, it became clear that conceptually day care staff saw the practices as ”very important, but not easily realised in practice”. As a result this demanded further research to address this issue and to extend this to the carefacility’s co-operation practises and their communal and social conditions. The research looks at the carefacility’s co-operation with key stakeholders. At the same time it undertakes an analytical and historical examination of carefacilitys’s with an experimental focus as two day care centres chosen as experimental objects. The results of the research showed that the benefits gained by children were determined by the day care centre’s socio-political structure and the parent’s resources. The research framework categorised early childhood education as generational and gender based structures. As part of the research, the strains endemic to these formations have been examined. The system for bringing up children was created as part of a so called welfare state project by implemented by the Day Care Act in year 1973. The law secured the subjective right for every pre-school child to have access to day care facilities. The law also introduced a labour and sosiopolitical phase and the refinement of the day care facility’s education-care concept. The latest phase that started during the early 1990´s was called the market-based social services strategy. As a result of this phase, state support was limited and the screening function of the law was relaxed. This new strategy resulted in a divisive and bureaucratic social welfare system, that individualised and segregated children and their parents, leaving some families outside the communal and welfare state benefit net. The modern day care centre is a hybrid of different aims. Children spend longer and more irregular time in day care. The families are multicultural and that requires more training for the staff. The work in day care has been enhanced, for example he level of education for the staff has been lowered and productivity has been improved. However, administrative work and different kinds of support and net work functions together with the continuous change have taken over from the work done face to face with children. Staff experiences more pressure as the management and the work load has increased. Consequently the long-term planning and daily implementation of the nuclear task of the day care facility is difficult to control. This will have an effect on both motivation and manageability of the work. Overall quality of the early childhood upbringing has been weakened. The possibilities for the near future were tested in the two day care centres chosen as an experi-ment objects. The analysis of these experiments showed that generative interaction work will benefit everyone: children, parents and employees. The main results of the research are new concepts of an early support day care centre, which can be empirically and theoretically possi-ble for development the near future. Key words: Day care facility’s co-operation practises, early childhood education as generational structure, child’s multi-operational and multi-layered community, multi-subjective operator, generative interaction work, communal composition.

Datorstödda studier i hälso- och socialvård : MuPSiNet-projektet

The aim of the study was to explore why the MuPSiNet project - a computer and network supported learning environment for the field of health care and social work - did not develop as expected. To grasp the problem some hypotheses were formulated. The hypotheses regarded the teachers' skills in and attitudes towards computing and their attitudes towards constructivist study methods. An online survey containing 48 items was performed. The survey targeted all the teachers within the field of health care and social work in the country, and it produced 461 responses that were analysed against the hypotheses. The reliability of the variables was tested using the Cronbach alpha coefficient and t-tests. Poor basic computing skills among the teachers combined with a vulnerable technical solution, and inadequate project management combined with lack of administrative models for transforming economic resources into manpower were the factors that turned out to play a decisive role in the project. Other important findings were that the teachers had rather poor skills and knowledge in computing, computer safety and computer supported instruction, and that these skills were significantly poorer among female teachers who were in majority in the sample. The fraction of teachers who were familiar with software for electronic patient records (EPR) was low. The attitudes towards constructivist teaching methods were positive, and further education seemed to utterly increase the teachers' readiness to use alternative teaching methods. The most important conclusions were the following: In order to integrate EPR software as a natural tool in teaching planning and documenting health care, it is crucial that the teachers have sufficient basic skills in computing and that more teachers have personal experience of using EPR software. In order for computer supported teaching to become accepted it is necessary to arrange with extensive further education for the teachers presently working, and for that further education to succeed it should be backed up locally among other things by sufficient support in matters concerning computer supported teaching. The attitudes towards computing showed significant gender differences. Based on the findings it is suggested that basic skills in computing should also include an awareness of data safety in relation to work in different kinds of computer networks, and that projects of this kind should be built up around a proper project organisation with sufficient resources. Suggestions concerning curricular development and further education are also presented. Conclusions concerning the research method were that reminders have a better effect, and that respondents tend to answer open-ended questions more verbosely in electronically distributed online surveys compared to traditional surveys. A method of utilising randomized passwords to guarantee respondent anonymity while maintaining sample control is presented. Keywords: computer-assisted learning, computer-assisted instruction, health care, social work, vocational education, computerized patient record, online survey

The Development of the Concept of Music Education in Estonian Kindergartens, 1905-2008 : a Historical–Critical Overview

The dissertation focuses on the development of music education in Estonian kindergartens and the factors influencing it, analysed in the historical perspective relying on post-positivist paradigm. The study is based on the factors and subjects’ views on kindergarten music education from 1905 to 2008, recorded in written sources or ascertained by means of questionnaire and interview. The dissertation deals with music’s functions, music education in retrospective, factors influencing child’s musical aptitude and development and teacher’s role in it through the prism of history. The formation of Estonian kindergarten music education and the phenomenon of its development have been researched by stages: the first manifestations of music in kindergarten in 1905 - 1940; the formation of the concept of music education in 1941 - 1967 and the application of a unified system in 1968 - 1990. The work also outlines innovative trends in music education at the end of the last millennium and the beginning of this century, in 1991 - 2008. The study relies on a combined design and an analysis of historical archival material and empirical data. The empirical part of the study is based on the questionnaire (n=183) and interviews (n=18) carried out with kindergarten music teachers. The data has been analysed using both qualitative and quantitative methods. The subject of the research is the content and activity types of kindergarten music education and the role of music teacher in their implementation. The study confirmed that fundamental changes took place in Estonian kindergarten music education due to the change in political power in the 1940s. Following the example of the Soviet system of education, music in kindergarten became an independent music educational orientation and the position of a professionally trained music teacher was established (1947). It was also confirmed that in the newly independent Estonian Republic under the influence of innovative trends a new paradigm of music education arose from the traditional singing-centred education towards the more balanced use of music activity types (attaching importance to the child-centred approach, an increase in the number and variety of activity types). The most important conclusions made in the dissertation are that there has been improvement and development deriving from contemporary trends in the clear concept that has evolved in Estonian kindergarten music education over a century; professionally trained music teachers have had a crucial role in shaping it; and kindergarten music education is firmly positioned as a part of preschool education in Estonian system of education. Key words: early childhood music education, history of music education, kindergarten music education, early childhood music teachers

Skogsbränslets elementära sammansättning med tanke på förbränningsprocessen och för näringsämnesförluster i ekosystemet

There are several reasons for increasing the usage of forest biomass for energy in Finland. Apart from the fact that forest biomass is a CO2 -neutral energy source, it is also a domestic resource distributed throughout the country. Usage of forest biomass in the form of logging residues decreases Finland’s dependence of energy import and increases both incomes and employment. Wood chips are mainly made from logging residues, which constitute 64 % of the raw material. A large-scale use of forest biomass requires heed also to the potential negative aspects. Forest bioenergy is used extensively, but its impacts on the forests soil nutrition and carbon balance has not been studied much. Nor have there been many studies on the heavy metal or chlorine content of logging residues. The goal of this study was to examine the content of carbon, macronutrients, heavy metals and other for the combustion harmful substances in Scots pine and Norway spruce wood chips, and to estimate the effect of harvesting of logging residues on the forests carbon and nutrient balance. Another goal was to examine the energy content of the clear cut remains. The Wood chips for this study were gathered from pine and spruce dominated clear cut sites in southern Finland, in the costal forests between Hankoo and Siuntio. The number of sample locations were 29, and the average area was 3,15 ha and the average timber volume 212,6 m3 ha -1. The average logged timber volume was for Scots pine timber 70 m3 ha -1 and for Norway spruce timber 124 m3 ha -1 and for deciduous timber (birch and alder) 18,5 m3 ha -1. The proportion of spruce in the logging residues and the stand-volume were relevant for how much nutrients were taken from the forest ecosystem when harvesting logging residues. In this study it was noted that the nutrient content of the logging residues clearly increased when the percentage of spruce in the timber volume increased. The S, K, Na and Cl -contents in the logging residues in this study increased with an increasing percentage of spruce, which is probably due to the fact that the spruce is an effective collector of atmospheric dry-deposition. The amounts of nutrients that were lost when harvesting logging residues were less than those referred to in the literature. Within a circulation period (100 years), the forest soil gets substantially more nutrients from atmospheric deposition, litter fall and weathering than is lost through harvesting of logging residues after a clear cut. Harvesting of the logging residues makes for a relatively modest increase of the quantity of carbon that is removed from the forest compared to traditional forestry. Due to the fact that the clear cut remains in my study showed a high content of chlorine, there is a risk of corrosion in connection to the incineration of the logging residues in power plants especially at coastal areas/forests. The risk of sulphur -related corrosion is probably rather small, because S concentrations are relatively low in woodchips. The clear cut remains showed rather high heavy metal contents. If the heavy metal contents in this study are representative for the clear cut remains in the coastal forests generally, there might be reason to exert some caution when using the ash for forest fertilizing purposes.

Novel Organo-Noble-Gas Hydrides

Noble gases are mostly known as inert monatomic gases due to their limited reactivity with other elements. However, the first predictions of noble-gas compounds were suggested by Kossel in 1916, by von Antropoff in 1924, and by Pauling in 1930. It took many decades until the first noble-gas compound, XePtF6, was synthesized by Neil Bartlett in 1962. This was followed by gradual development of the field and many noble-gas compounds have been prepared. In 1995, a family of noble-gas hydride molecules was discovered at the University of Helsinki. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. The first molecular species made include HXeI, HXeBr, HXeCl, HKrCl and HXeH. Nowadays the total number of prepared HNgY molecules is 23 including both inorganic and organic compounds. The first and only neutral ground-state argon compound, HArF, was synthetized in 2000. Helium and neon are the only elements in the periodic table that do not form neutral, ground-state molecules. In this Thesis, experimental preparation of eight novel xenon- and krypton-containing organo-noble-gas hydrides made from acetylene (HCCH), diacetylene (HCCCCH) and cyanoacetylene (HCCCN) are presented. These novel species include the first organic krypton compound, HKrCCH, as well as the first noble-gas hydride molecule containing two Xe atoms, HXeCCXeH. Other new compounds are HXeCCH, HXeCC, HXeC4H, HKrC4H, HXeC3N, and HKrC3N. These molecules are prepared in noble-gas matrices (krypton or xenon) using ultraviolet photolysis of the precursor molecule and thermal mobilization of the photogenerated H atoms. The molecules were identified using infrared spectroscopy and ab initio calculations. The formation mechanisms of the organo-noble-gas molecules are studied and discussed in this context. The focus is to evidence experimentally the neutral formation mechanisms of HNgY molecules upon global mobility of H atoms. The formation of HXeCCXeH from another noble-gas compound (HXeCC) is demonstrated and discussed. Interactions with the surrounding matrix and molecular complexes of the HXeCCH molecule are studied. HXeCCH was prepared in argon and krypton solids in addition to a Xe matrix. The weak HXeCCH∙∙∙CO2 complex is prepared and identified. Preparation of the HXeCCH∙∙∙CO2 complex demonstrates an advanced approach to studies of HNgY complexes where the precursor complex (HCCH∙∙∙CO2) is obtained using photolysis of a larger molecule (propiolic acid).

Radikalcyklisering vid syntes av polycykliska indoler och pyrroler

I de senaste två decennierna har radikalcyklisering, intramolekylär radikaladdition, utvecklats till en viktig syntesmetod för polycykliska indoler och pyrroler. De erhållna produktmolekylerna eller deras derivat är ofta naturliga eller syntetiska alkaloider som väckt biologiskt eller medicinskt intresse. Avhandlingen behandlar både intramolekylära radikaladditioner av pyrrolyl-, indolyl- eller indolylacylradikaler till -bindningar och intramolekylära additioner av flera olika radikaler till indolens eller pyrrolens -system. Också cykliseringar som delreaktioner i radikalkaskader behandlas. Radikalreaktioner kan släckas både oxidativt och reduktivt. För att bibehålla heteroarenens aromaticitet måste cykliseringar till pyrrol- eller indolringen släckas oxidativt. Oxidativa radikaladditioner till aromater benämns homolytiska aromatiska substitutioner. Det finns olika sätt att erhålla en reaktantradikal från en radikalprekursor. I vissa fall har radikalprekursorn en mycket labil bindning som kan brytas fotokemiskt eller med hjälp av en initiator. Till exempel kol-svavelbindningen av en O-etyl-S-alkylxanthat kan brytas på detta sätt. Ofta används dock en radikalmediator för att bilda en reaktantradikal från dess prekursor. Mediatorer är ofta föreningar, som under reaktionsförhållandena själv bildar radikaler med en stor affinitet för en prekursors specifika atom eller atomgrupp vilken abstraheras. Således fungerar mediatorn som mellanhand vid bildning av reaktantradikalen. Exempel på mediatorer av detta slag som använts vid syntes av polycykliska pyrroler och indoler är tributyltennhydrid, hexabutylditenn, tris(trimetylsilyl)silan, tributylgermaniumhydrid, dicumylperoxid, trietylboran, natriumarensulfinater (med ättiksyra) och Se-fenyl-p-toluenselenosulfonat. Också dimetylsulfoxid kan ses som mediator då den bildar metylradikaler vid Fentonreaktion i lösningsmedlet. Övergångsmetallsalter kan även bilda reaktantradikalen från prekursorn genom enelektronoxidationer eller -reduktioner. Vid syntes av polycykliska pyrroler och indoler har reaktantradikalen bildats genom enelektronoxidationer med Mn(OAc)3 eller Ag2+ (Miniscireaktion) och elektronreduktioner med ett Ni(I)-komplex eller SmI2. Avhandlingen är indelad enligt reagenset eller reagensen, som åstadkommer bildning av reaktantradikalen vid syntes av polycykliska indoler och pyrroler. Cirka hälften av avhandlingen behandlar tributyltennhydridmedierade cykliseringar då reagenset trots dess toxicitet är det överlägset mest använda. Avhandlingen diskuterar mekanismen för bildning av reaktantradikalen från prekursorn, cykliseringen och dess möjliga regioselektivitet, andra radikalreaktioner vid radikalkaskader och hur produktradikalen släcks.

Komplexa tal - vad är det?

Komplexa tal har traditionellt undervisats i de finländska gymnasierna som en valbar kurs. Denna situation har förändrats i och med de nya läroplanerna som tagits i bruk senast hösten 2005. Den nya, striktare läroplanen ger inte lika stora valmöjligheter för skolorna att bestämma undervisningsstoffet, inte ens för de valbara kurserna, och därför har många gymnasier varit tvungna att sluta undervisa om komplexa tal. För att fortsättningsvis ge en möjlighet för gymnasieelever att studera komplexa tal finns detta kompendium. Kompendiet fyller två syften. I de gymnasier där komplexa tal fortfarande finns med i läroplanen kan kompendiet användas som läromedel på ifrågavarande kurs. Kompendiet torde vara önskat eftersom det inte existerar något modernt, finlandssvenskt läromedel där de komplexa talen tas upp. Kompendiets andra, huvudsakliga syfte är att finnas till att ge en möjlighet för de elever, som inte går ett gymnasium där komplexa tal undervisas, att på egen hand lära sig grunder om komplexa tal. Kunskap om utvidgandet av talområdet från reella talen till komplexa hör till matematisk allmänbildning, och är till stor nytta om man är intresserad av att fortsätta studera matematik eller naturvetenskaper efter gymnasiet. Kompendiet kommer att läggas ut på nätet för att få det lättillgängligt. I det första kapitlet behandlas matematikens uppkomst. Det andra kapitlet är en introduktion till varför man behöver komplexa tal, där gås tal- och mängdlära igenom samtidigt som de i kompendiet använda beteckningarna introduceras. I det tredje kapitlet behandlas de komplexa talen; grundläggande räkneregler, absolutbelopp och argument, komplexa tal i polär form och lösning till högregradsekvationer är centrala begrepp. de Moivers formel är ett av de viktigare målen, även Eulers formel behandlas kort. Problematik med negativa kvadratrötter tas också upp. Det fjärde kapitlet handlar om de komplexa talens intressanta historia. I kompendiet finns rikligt med exempel och övningsuppgifter. Kapitel fem innehåller extra övningsuppgifter och i kapitel sex finns lösningarna till samtliga uppgifter. Trots att kompendiets omfång avsevärt ökas i och med dessa lösningar är det av värde att de finns med för att kompendiets huvudsakliga syfte skall uppfyllas: att eleverna på egen hand skall kunna lära sig stoffet.