Tailoring polyolefin properties by metallocene catalysis

This doctoral thesis deals with the syntheses of olefin homo- and copolymers using different kind of metallocene catalyst. Ethene, propene, 1-hexene, 1-hexadecene, vinylcyclohexane and phenylnorbornene were homo- or copolymerized with the catalysts. The unbridged benzyl substituted zirconium dichloride catalysts (1-4), ansa- bridged acenaphtyl substituted zirconium dichloride catalysts, ( 5, 6), rac- and meso-ethylene-bis(1-indenyl)zirconium dichlorides, (rac- and meso-8), rac-ethylene-bis(1-indenyl)hafnium dichloride, ( 12), bis(9-fluorenyl)hafnium dichloride (14 ) enantiomerically pure (R)- phenylethyl[(9-fluorenyl-1-indenyl)]ZrCl2, (11), 14 and asymmetric dimethylsilyl[(3-benzylindenyl-(2-methylbenzen[e]indenyl)] zirconium dichloride, (13), were prepared in our laboratory. Dimethylsilyl-bis(1-indenyl)zirconium dichloride, (9), isopropylidene(9-fluorenyl-cyclopentadienyl)zirconium dichloride, (10), and were obtained commercially. The solid-state structures of the catalysts rac- and meso-1 were determined by X-ray crystallography. Computational methods were used for the structure optimization of the catalyst rac- and meso-1 in order to compare the theoretical calculations with the experimental results. Polymerization experiments were conducted in a highly purified autoclave system using low pressures (< 5 bar) of gaseous monomers. The experiments were designed to attain the optimal catalytic activity and a uniform copolymer composition. The prepared homo- and copolymers were characterized by the gel permeation chromatography, GPC, differential scanning calorimetry, DSC, nuclear magnetic resonance, NMR, and Fourier transform infrared spectrometry, FTIR . Molar mass (Mw, Mn), molar mass distribution (Mw/Mn), tacticity, comonomer content, melting temperature, glass transition temperature, and end group structures and content were determined. A special attention was paid on the correlation of the polymer properties with the catalyst structures and polymerization conditions. An intramolecular phenyl coordination was found in phenyl substituted benzyl zirconocenes 1-3 explaining the decreased activity of the catalysts. Novel copolymers poly(propene-co-phenylnorbornene) and poly(propene co-vinylcyclohexane), were synthesized and high molar mass poly(ethene-co-1-hexene) and poly(ethene-co-1-hexadecene) copolymers with elastic properties were prepared. Activation of a hafnocene catalyst was studied with UV-Vis spectrometry and activation process for the synthesis of ultra high molar mass poly(1-hexene) was found out.

Polymer Protected Gold Nanoparticles

Polymer protected gold nanoparticles have successfully been synthesized by both "grafting-from" and "grafting-to" techniques. The synthesis methods of the gold particles were systematically studied. Two chemically different homopolymers were used to protect gold particles: thermo-responsive poly(N-isopropylacrylamide), PNIPAM, and polystyrene, PS. Both polymers were synthesized by using a controlled/living radical polymerization process, reversible addition-fragmentation chain transfer (RAFT) polymerization, to obtain monodisperse polymers of various molar masses and carrying dithiobenzoate end groups. Hence, particles protected either with PNIPAM, PNIPAM-AuNPs, or with a mixture of two polymers, PNIPAM/PS-AuNPs (i.e., amphiphilic gold nanoparticles), were prepared. The particles contain monodisperse polymer shells, though the cores are somewhat polydisperse. Aqueous PNIPAM-AuNPs prepared using a "grafting-from" technique, show thermo-responsive properties derived from the tethered PNIPAM chains. For PNIPAM-AuNPs prepared using a "grafting-to" technique, two-phase transitions of PNIPAM were observed in the microcalorimetric studies of the aqueous solutions. The first transition with a sharp and narrow endothermic peak occurs at lower temperature, and the second one with a broader peak at higher temperature. In the first transition PNIPAM segments show much higher cooperativity than in the second one. The observations are tentatively rationalized by assuming that the PNIPAM brush can be subdivided into two zones, an inner and an outer one. In the inner zone, the PNIPAM segments are close to the gold surface, densely packed, less hydrated, and undergo the first transition. In the outer zone, on the other hand, the PNIPAM segments are looser and more hydrated, adopt a restricted random coil conformation, and show a phase transition, which is dependent on both particle concentration and the chemical nature of the end groups of the PNIPAM chains. Monolayers of the amphiphilic gold nanoparticles at the air-water interface show several characteristic regions upon compression in a Langmuir trough at room temperature. These can be attributed to the polymer conformational transitions from a pancake to a brush. Also, the compression isotherms show temperature dependence due to the thermo-responsive properties of the tethered PNIPAM chains. The films were successfully deposited on substrates by Langmuir-Blodgett technique. The sessile drop contact angle measurements conducted on both sides of the monolayer deposited at room temperature reveal two slightly different contact angles, that may indicate phase separation between the tethered PNIPAM and PS chains on the gold core. The optical properties of amphiphilic gold nanoparticles were studied both in situ at the air-water interface and on the deposited films. The in situ SPR band of the monolayer shows a blue shift with compression, while a red shift with the deposition cycle occurs in the deposited films. The blue shift is compression-induced and closely related to the conformational change of the tethered PNIPAM chains, which may cause a decrease in the polarity of the local environment of the gold cores. The red shift in the deposited films is due to a weak interparticle coupling between adjacent particles. Temperature effects on the SPR band in both cases were also investigated. In the in situ case, at a constant surface pressure, an increase in temperature leads to a red shift in the SPR, likely due to the shrinking of the tethered PNIPAM chains, as well as to a slight decrease of the distance between the adjacent particles resulting in an increase in the interparticle coupling. However, in the case of the deposited films, the SPR band red-shifts with the deposition cycles more at a high temperature than at a low temperature. This is because the compressibility of the polymer coated gold nanoparticles at a high temperature leads to a smaller interparticle distance, resulting in an increase of the interparticle coupling in the deposited multilayers.

Comprehensive Two-Dimensional Gas Chromatography: Instrumental and Methodological Development

Comprehensive two-dimensional gas chromatography (GC×GC) offers enhanced separation efficiency, reliability in qualitative and quantitative analysis, capability to detect low quantities, and information on the whole sample and its components. These features are essential in the analysis of complex samples, in which the number of compounds may be large or the analytes of interest are present at trace level. This study involved the development of instrumentation, data analysis programs and methodologies for GC×GC and their application in studies on qualitative and quantitative aspects of GC×GC analysis. Environmental samples were used as model samples. Instrumental development comprised the construction of three versions of a semi-rotating cryogenic modulator in which modulation was based on two-step cryogenic trapping with continuously flowing carbon dioxide as coolant. Two-step trapping was achieved by rotating the nozzle spraying the carbon dioxide with a motor. The fastest rotation and highest modulation frequency were achieved with a permanent magnetic motor, and modulation was most accurate when the motor was controlled with a microcontroller containing a quartz crystal. Heated wire resistors were unnecessary for the desorption step when liquid carbon dioxide was used as coolant. With use of the modulators developed in this study, the narrowest peaks were 75 ms at base. Three data analysis programs were developed allowing basic, comparison and identification operations. Basic operations enabled the visualisation of two-dimensional plots and the determination of retention times, peak heights and volumes. The overlaying feature in the comparison program allowed easy comparison of 2D plots. An automated identification procedure based on mass spectra and retention parameters allowed the qualitative analysis of data obtained by GC×GC and time-of-flight mass spectrometry. In the methodological development, sample preparation (extraction and clean-up) and GC×GC methods were developed for the analysis of atmospheric aerosol and sediment samples. Dynamic sonication assisted extraction was well suited for atmospheric aerosols collected on a filter. A clean-up procedure utilising normal phase liquid chromatography with ultra violet detection worked well in the removal of aliphatic hydrocarbons from a sediment extract. GC×GC with flame ionisation detection or quadrupole mass spectrometry provided good reliability in the qualitative analysis of target analytes. However, GC×GC with time-of-flight mass spectrometry was needed in the analysis of unknowns. The automated identification procedure that was developed was efficient in the analysis of large data files, but manual search and analyst knowledge are invaluable as well. Quantitative analysis was examined in terms of calibration procedures and the effect of matrix compounds on GC×GC separation. In addition to calibration in GC×GC with summed peak areas or peak volumes, simplified area calibration based on normal GC signal can be used to quantify compounds in samples analysed by GC×GC so long as certain qualitative and quantitative prerequisites are met. In a study of the effect of matrix compounds on GC×GC separation, it was shown that quality of the separation of PAHs is not significantly disturbed by the amount of matrix and quantitativeness suffers only slightly in the presence of matrix and when the amount of target compounds is low. The benefits of GC×GC in the analysis of complex samples easily overcome some minor drawbacks of the technique. The developed instrumentation and methodologies performed well for environmental samples, but they could also be applied for other complex samples.

The Interplays of Histories, Economies and Cultures in Human Adaptation and Settlement Patterns : The Cases of the Faroe Islands and Greenland

The Arctic peoples are currently faced with the challenge of adapting to climate change. Adaptive strategies have been central for the survival of the Northern communities also in the past. This doctoral dissertation is a comparative study of how two Northern societies, the Faroe Islands and Greenland, have responded to challenges caused by the interplay of environmental, political and socio-economic changes. Its main objective is to describe the characteristics of respective adaptive strategies developed in the two societies and to show which connections exist between adaptation and the development of the settlement patterns. This study is based on document analysis, supported by an analysis of demographic and economic statistics. For the field work, the empirical method of landscape-reading was applied. A narrative approach was used to explain interrelations between adaptive strategies and societal developments in the Faroe Islands and Greenland. Maps illustrating development and changes in settlement patterns in different time periods are central for this study because they illustrate the impacts of adaptation on settlement development. The results of this dissertation show that people in the Faroe Islands and Greenland have consciously developed their settlements and used this as an adaptive strategy: different types of settlements were established depending on which kind of resource base was available. Strong dependency on a single resource is likely to increase the probability that settlement development was impacted by it. The interrelation of natural resource use and settlement pattern development has weakened in the Faroe Islands and Greenland from the mid-1900s. Since then, the importance of the government settlement policies has become pronounced and the existing settlement pattern, including settlements without prospects for genuine economic viability, has been preserved. Currently, the Northern communities are increasingly dependent on worldwide developments. In the light of this study, the communities can respond to challenges of globalization and climate change and develop new kind of adaptive strategies, such as diversification of their economic activities. This dissertation shows that it is important to extend studies about community adaptation in the High North to consider the overall development of the Northern settlement patterns.

Geological factors affecting on after-use of Finnish cut-over peatlands : with implications on the carbon accumulation

In Finland, peat harvesting sites are utilized down almost to the mineral soil. In this situation the properties of mineral subsoil are likely to have considerable influence on the suitability for the various after-use forms. The aims of this study were to recognize the chemical and physical properties of mineral subsoils possibly limiting the after-use of cut-over peatlands, to define a minimum practice for mineral subsoil studies and to describe the role of different geological areas. The future percentages of the different after-use forms were predicted, which made it possible to predict also carbon accumulation in this future situation. Mineral subsoils of 54 different peat production areas were studied. Their general features and grain size distribution was analysed. Other general items studied were pH, electrical conductivity, organic matter, water soluble nutrients (P, NO3-N, NH4-N, S and Fe) and exchangeable nutrients (Ca, Mg and K). In some cases also other elements were analysed. In an additional case study carbon accumulation effectiveness before the intervention was evaluated on three sites in Oulu area (representing sites typically considered for peat production). Areas with relatively sulphur rich mineral subsoil and pool-forming areas with very fine and compact mineral subsoil together covered approximately 1/5 of all areas. These areas were unsuitable for commercial use. They were recommended for example for mire regeneration. Another approximate 1/5 of the areas included very coarse or very fine sediments. Commercial use of these areas would demand special techniques - like using the remaining peat layer for compensating properties missing from the mineral subsoil. One after-use form was seldom suitable for one whole released peat production area. Three typical distribution patterns (models) of different mineral subsoils within individual peatlands were found. 57 % of studied cut-over peatlands were well suited for forestry. In a conservative calculation 26% of the areas were clearly suitable for agriculture, horticulture or energy crop production. If till without large boulders was included, the percentage of areas suitable to field crop production would be 42 %. 9-14 % of all areas were well suitable for mire regeneration or bird sanctuaries, but all areas were considered possible for mire regeneration with correct techniques. Also another 11 % was recommended for mire regeneration to avoid disturbing the mineral subsoil, so total 20-25 % of the areas would be used for rewetting. High sulphur concentrations and acidity were typical to the areas below the highest shoreline of the ancient Litorina sea and Lake Ladoga Bothnian Bay zone. Also differences related to nutrition were detected. In coarse sediments natural nutrient concentration was clearly higher in Lake Ladoga Bothnian Bay zone and in the areas of Svecokarelian schists and gneisses, than in Granitoid area of central Finland and in Archaean gneiss areas. Based on this study the recommended minimum analysis for after-use planning was for pH, sulphur content and fine material (<0.06 mm) percentage. Nutrition capacity could be analysed using the natural concentrations of calcium, magnesium and potassium. Carbon accumulation scenarios were developed based on the land-use predictions. These scenarios were calculated for areas in peat production and the areas released from peat production (59300 ha + 15 671 ha). Carbon accumulation of the scenarios varied between 0.074 and 0.152 million t C a-1. In the three peatlands considered for peat production the long term carbon accumulation rates varied between 13 and 24 g C m-2 a-1. The natural annual carbon accumulation had been decreasing towards the time of possible intervention.

On Random Planar Curves and Their Scaling Limits

Planar curves arise naturally as interfaces between two regions of the plane. An important part of statistical physics is the study of lattice models. This thesis is about the interfaces of 2D lattice models. The scaling limit is an infinite system limit which is taken by letting the lattice mesh decrease to zero. At criticality, the scaling limit of an interface is one of the SLE curves (Schramm-Loewner evolution), introduced by Oded Schramm. This family of random curves is parametrized by a real variable, which determines the universality class of the model. The first and the second paper of this thesis study properties of SLEs. They contain two different methods to study the whole SLE curve, which is, in fact, the most interesting object from the statistical physics point of view. These methods are applied to study two symmetries of SLE: reversibility and duality. The first paper uses an algebraic method and a representation of the Virasoro algebra to find common martingales to different processes, and that way, to confirm the symmetries for polynomial expected values of natural SLE data. In the second paper, a recursion is obtained for the same kind of expected values. The recursion is based on stationarity of the law of the whole SLE curve under a SLE induced flow. The third paper deals with one of the most central questions of the field and provides a framework of estimates for describing 2D scaling limits by SLE curves. In particular, it is shown that a weak estimate on the probability of an annulus crossing implies that a random curve arising from a statistical physics model will have scaling limits and those will be well-described by Loewner evolutions with random driving forces.

Mathematical Aspects of Financial Markets with Frictions

Frictions are factors that hinder trading of securities in financial markets. Typical frictions include limited market depth, transaction costs, lack of infinite divisibility of securities, and taxes. Conventional models used in mathematical finance often gloss over these issues, which affect almost all financial markets, by arguing that the impact of frictions is negligible and, consequently, the frictionless models are valid approximations. This dissertation consists of three research papers, which are related to the study of the validity of such approximations in two distinct modeling problems. Models of price dynamics that are based on diffusion processes, i.e., continuous strong Markov processes, are widely used in the frictionless scenario. The first paper establishes that diffusion models can indeed be understood as approximations of price dynamics in markets with frictions. This is achieved by introducing an agent-based model of a financial market where finitely many agents trade a financial security, the price of which evolves according to price impacts generated by trades. It is shown that, if the number of agents is large, then under certain assumptions the price process of security, which is a pure-jump process, can be approximated by a one-dimensional diffusion process. In a slightly extended model, in which agents may exhibit herd behavior, the approximating diffusion model turns out to be a stochastic volatility model. Finally, it is shown that when agents' tendency to herd is strong, logarithmic returns in the approximating stochastic volatility model are heavy-tailed. The remaining papers are related to no-arbitrage criteria and superhedging in continuous-time option pricing models under small-transaction-cost asymptotics. Guasoni, Rásonyi, and Schachermayer have recently shown that, in such a setting, any financial security admits no arbitrage opportunities and there exist no feasible superhedging strategies for European call and put options written on it, as long as its price process is continuous and has the so-called conditional full support (CFS) property. Motivated by this result, CFS is established for certain stochastic integrals and a subclass of Brownian semistationary processes in the two papers. As a consequence, a wide range of possibly non-Markovian local and stochastic volatility models have the CFS property.

XML Messaging for Mobile Devices

In recent years, XML has been widely adopted as a universal format for structured data. A variety of XML-based systems have emerged, most prominently SOAP for Web services, XMPP for instant messaging, and RSS and Atom for content syndication. This popularity is helped by the excellent support for XML processing in many programming languages and by the variety of XML-based technologies for more complex needs of applications. Concurrently with this rise of XML, there has also been a qualitative expansion of the Internet's scope. Namely, mobile devices are becoming capable enough to be full-fledged members of various distributed systems. Such devices are battery-powered, their network connections are based on wireless technologies, and their processing capabilities are typically much lower than those of stationary computers. This dissertation presents work performed to try to reconcile these two developments. XML as a highly redundant text-based format is not obviously suitable for mobile devices that need to avoid extraneous processing and communication. Furthermore, the protocols and systems commonly used in XML messaging are often designed for fixed networks and may make assumptions that do not hold in wireless environments. This work identifies four areas of improvement in XML messaging systems: the programming interfaces to the system itself and to XML processing, the serialization format used for the messages, and the protocol used to transmit the messages. We show a complete system that improves the overall performance of XML messaging through consideration of these areas. The work is centered on actually implementing the proposals in a form usable on real mobile devices. The experimentation is performed on actual devices and real networks using the messaging system implemented as a part of this work. The experimentation is extensive and, due to using several different devices, also provides a glimpse of what the performance of these systems may look like in the future.

Computing the Stochastic Complexity of Simple Probabilistic Graphical Models

Minimum Description Length (MDL) is an information-theoretic principle that can be used for model selection and other statistical inference tasks. There are various ways to use the principle in practice. One theoretically valid way is to use the normalized maximum likelihood (NML) criterion. Due to computational difficulties, this approach has not been used very often. This thesis presents efficient floating-point algorithms that make it possible to compute the NML for multinomial, Naive Bayes and Bayesian forest models. None of the presented algorithms rely on asymptotic analysis and with the first two model classes we also discuss how to compute exact rational number solutions.

Scrum-prosessimallin käyttöliittymäriskien minimointi simulointipohjaisella GDD-käyttöliittymäsuunnittelumenetelmällä

Scrum-prosessimalli jättää menettelyt ohjelmiston käyttöliittymän tuottamiseen auki ja käyttöliittymä syntyy pahimmillaan toimintolistan pohjalta ohjelmoinnin sivutuotteena. Näin syntynyt järjestelmä soveltuu suurella riskillä huonosti käyttötarkoitukseensa. Tässä tutkielmassa analysoitiin Scrum-prosessimallin käyttöliittymäriskikohtia, joita löytyi kolme: asiakkaan toivomat ominaisuudet päätyvät sellaisinaan ohjelmiston vaatimuksiksi, toimintolistan pohjalta syntyy käytettävyydeltään heikkoja käyttöliittymäratkaisuja ja käyttöliittymän arviointi sprintin katselmoinnissa tuottaa epäluotettavia tuloksia. Tutkielmassa käsitellään Scrum-prosessimallin käyttöliittymäriskien minimointia simulointipohjaisella GDD-käyttöliittymäsuunnittelulla. Riskien minimointia tarkastellaan esimerkkitapauksen avulla, jossa ohjelmistoyritys Reaktor toteutti ammattikorkeakoulun toiminnansuunnittelujärjestelmän vuosisuunnitteluosion. Esimerkkitapauksessa Scrumin käyttöliittymäriskit saatiin minimoitua selvittämällä loppukäyttäjien käyttötilanteet kontekstuaalisilla haastatteluilla, suunnittelemalla käyttöliittymä GDD-menetelmällä ja arvioimalla käyttöliittymää hyödyllisyysläpikäynneillä. Alkuperäisessä Scrumissa liiketoiminnallisesta kannattavuudesta vastaava tuotteen omistaja ja toteutustiimi ottavat vastuulleen myös käyttöliittymän toimintalogiikan. GDD:n myötä vastuu toimintalogiikasta siirretään käyttöliittymäsuunnittelijalle, jolloin Scrumin roolit muuttuvat. Tässä työssä käsitellään GDD-käyttöliittymäsuunnittelun tuomat muutokset Scrumin rooleihin ja käytäntöihin. Scrumin käyttöliittymäriskien minimoinnin jälkeen toteutusvaiheeseen jää vielä Scrumista riippumattomia käyttöliittymäriskejä. Tämän työn esimerkkitapauksessa keskeisin näistä oli käyttöliittymätoteutukseen päätyneet puutteelliset interaktiot. Riski eliminoitiin hyväksymismenettelyllä, jossa ohjelmoija antaa toteutetun ominaisuuden käyttöliittymäsuunnittelijalle tarkistettavaksi. Hyväksymismenettelyn avulla projektin työnjako selkiytyi, toteutustyön laatu parani ja toteutustiimin ja käyttöliittymäsuunnittelijoiden välinen kommunikaatio tehostui.

Spirituality of Finnish peacekeepers

The previous academic research on Finnish peacekeeping has clarified the operative and historical aspects of Finnish peacekeeping lacking the view of an individual who does the actual peacekeeping work. This research is based on the underlying theoretical assumption of human beings possessing different kinds of talents and intelligences creating a holistic entity. In this broad perspective spirituality was explored as an umbrella concept, as a holistic ability or talent, that can be explored as the deepest aspect of defining what it means to be human. The theoretical framework incorporated the concept of an intelligence, which is defined in Gardner's theory of multiple intelligences as the ability to solve problems, or to create products, that are valued within one or more cultural settings (Gardner, 1993, x). The viability of this theory was studied in the sample of Finnish peacekeepers. Spirituality in the theoretical and conceptual horizon was viewed as an extension of Gardner's theory of intelligences as one potential Gardnerian intelligence candidate. In addition to Gardner's theory, spirituality was explored as sensitivity which includes capacities such as sensing awareness, sensing mystery and sensing value (Hay, 1998). Also the practical aspects of spirituality were taken in account as shown in our everyday lives giving us the direction and influencing our social responsibilities and concerns (Bradford, 1995). Spirituality was explored also involving the element of the peacekeepers' community, the element of personal moral orientations and in the domain of religion and coping. The purpose of this research aimed in two dimensions. First, the aim was to outline the intelligence profile and the spiritual sensitivity profile of peacekeepers. Second, the aim was to understand qualitatively the nature of peacekeepers' spirituality The research interests were studied with different kinds of peacekeepers. Applying the mixed methods approach the research was conducted in two phases: first the former SFOR peacekeepers (N=6) were interviewed and the data was analysed. Inspired by the primary findings of these interviews, the data for the case-study of one peacekeeper was collected in co-operation with one former SFOR peacekeeper (N=1). In the second phase the data was collected from KFOR peacekeepers through the quantitative MI-Survey and the spiritual sensitivity survey (N=195). The quantitative method was used to outline the intelligence profile and the spiritual sensitivity profile of peacekeepers (N=195). In the mixed methods approach this method highlighted the general overview of intelligence traits and spiritual sensitivity of peacekeepers. In the mixed methods approach the qualitative method including interviews (N=6) and a case-study of one peacekeeper (N=1) increased subjective, qualitative information of spirituality of peacekeepers. The intelligence profile of peacekeepers highlighted the bodily-kinesthetic and interpersonal dimensions as the practical and social aspects of peacekeepers. Strong inter-item dependencies in the intrapersonal intelligence profile meant that peacekeepers possess a self-reflection and self-knowledge component and they reflect on deep psychological and philosophical issues. Regarding the spiritual sensitivity, peacekeepers found awareness-sensing, mystery-sensing, value-sensing and community-sensing important. The community-sensing emphasised a strong will to advance peace and to help people who are in need: things that are close to the heart of the peacekeepers. These results depicted practicality, being socially capable, and reflecting one's inner world as essential to peacekeepers. Moreover, spirituality as peacekeepers' moral endeavour became clearer because the sub-model of their community-sensing described morally charged destinations: advancing peace and helping people in need. In the qualitative findings peacekeepers articulated justice orientation and rule-following characterising the nature of peacekeepers' moral attitude and moral call (Kohlberg, 1969). An ethic of care (Gilligan, 1982) describes mainly female moral orientation, but the findings revealed that an ethic of care is also an important agent supporting strongly male peacekeepers in their aim to carry out qualitatively good peacekeeping work. The moral endeavour was voiced, when the role of religion in coping meant the assessment of the a way of life, a way of conduct, a way of being truthful to one's own values in confusing surroundings. The practical level of spiritual and religious contemplation was voiced as morally charged inner motivation to fulfil one's duties and at the same time to cope with various peacekeeping challenges. The results of different data sets were combined and interpreted as the moral endeavour, which characterises peacekeepers' spirituality. As the combining result, the perspective of peacekeepers' spirituality is considered moral or at least morally charged.

Hyvän hoidon reuna-alueilla : Potilasvahinko lääketieteellisen toiminnan valossa.

Vuonna 2006 Suomessa korvattiin 2331 potilasvahinkoa. Niistä maksettiin korvauksia yhteensä noin 27 miljoonaa euroa. Tässä tutkimuksessa tarkastellaan potilasvahinkoja lääketieteellisen toiminnan valossa. Tutkimuksessa pyritään vastaamaan kysymykseen: Millä eri tavoilla lääkärin toiminta voi epäonnistua potilasvahinkotapauksissa? Tutkimuksessa määriteltiin neljä kategoriaa, joiden avulla analysoitiin esimerkkitapauksia. Kategoriat käsittelivät hoitojärjestelmää, lääkärin toimintaan vaikuttavia normeja, toiminnan intentionaalisuutta sekä toiminnan suhdetta sen lopputuloksiin ja seurauksiin. Ensimmäisessä tutkimusluvussa määriteltiin kategoriat, joiden avulla lääketieteellistä toimintaa voi arvioida. Ensimmäiseksi analysoitiin hoitojärjestelmää, lääkärin toiminnan kontekstia. Hoitojärjestelmästä nostettiin esille potilas-lääkärisuhde, lääkärien välinen yhteistyö, potilaasta saatavat tiedot, toiminnan mahdollistavat resurssit sekä niin kutsuttu systeemivirhe. Hoitojärjestelmän toimiminen on hyvän hoidon ensimmäinen edellytys. Se vaatii eri terveydenhuollon ammattihenkilöiden saumatonta yhteistyötä.Toinen kategoria käsitteli lääkärin toimintaan vaikuttavia normeja. Georg Henrik von Wrightin teoksen Norm and Action normien jaottelua sovellettiin lääkärin toimintaan. Normien pääryhmään kuuluvat säännöt, määräykset ja ohjeet. Lisäksi voidaan määritellä pienempiä normiryhmiä, jotka sijaitsevat pääryhmien välimaastossa. Näihin pienempiin ryhmiin sijoittuvat tottumukset, moraaliset periaatteet sekä ideaalit säännöt. Kolmannessa kategoriassa käsiteltiin intentionaalisuutta osana toimintaa. Teorian päälähde oli G. E. M. Anscomben teos Intention. Toiminnan intentionaalisuutta analysoitiin Anscomben tunnetun, vesikaivon myrkytystä koskevan, esimerkin avulla. Siinä tekoon liittyvä sisäinen tieto on keskeinen intentiota määrittävä tekijä. Viimeisessä kategoriassa arvioitiin toimintaa von Wrightin mukaan. Esille nousi erityisesti kyky toiminnan perusedellytyksenä sekä toiminnan lopputulos ja seuraukset. Potilasvahingoissa on tärkeää arvioida myös potilasvahingon seurauksia, ei vain epäonnistuneen toimenpiteen lopputulosta. Toimintaa analysoitaessa oli myös otettava huomioon kenen näkökulmasta seurauksia arvioitiin, Potilas, lääkäri ja esimerkiksi osastonylilääkäri saattavat nähdä potilasvahingon seuraukset hyvin eri tavoilla.Toisessa tutkimusluvussa arvioitiin neljää Terveydenhuollon oikeusturvakeskuksen ja lääninhallitusten sosiaali- ja terveysosastojen kantelu- ja valvontaratkaisuista valittua esimerkkitapausta. Ensimmäinen käsitteli lääkärin toiminnan epäonnistumista synnytyksessä, toinen psyykkisistä ongelmista ja alkoholiriippuvuudesta kärsivän lääkärin ammatinharjoittamisoikeuksien rajoittamista, kolmas lääketutkimuksen johtajan vakavia virheitä ja neljäs Terveydenhuollon oikeusturvakeskuksen pysyvän asiantuntijan ristiriitaisia asiantuntijalausuntoja. Lääkärin toiminnan epäonnistuminen vaikuttaa helposti hoitojärjestelmään, jonka toimiminen perustuu työntekijöiden yhteistyöhön. Hoitovirheissä rikotaan yleensä lääketieteen sääntöjä. Potilasvahingon sattuessa lääkärin asema muuttuu normiauktoriteetista normisubjektiksi. Lääkäri saattaa toiminnallaan rikkoa myös moraalisia sääntöjä tai lääkärin ihannetta. Puhtaissa vahinkotapauksissa toiminnan lopputulos ei vastaa lääkärin intentiota, potilaan parantamista. Kaikissa potilasvahinkotapauksissa ei voida puhua vahingoista, vaan kyseessä voi olla myös tarkoituksellinen teko. Toiminnan lopputuloksella voi olla laajat seuraukset, jotka tulisi myös ottaa huomioon toimintaa arvioitaessa.

Rauhallisen yhteiselämän ohjeet : Avioliitto ja puolisoiden roolit Plutarkhoksella ja Uuden testamentin ajan kristillisessä kirjallisuudessa

Plutarkhoksen ja Uuden testamentin ajan kristillisten kirjoittajien naiskuvaa ja näkemystä avioliitosta ei ole juurikaan vertailtu aiemmin. Molempien teokset on kirjoitettu suunnilleen samoihin aikoihin ja ne esittävät samanlaisen eettisen ideaalin avioliitosta ja puolisoiden rooleista siinä. Plutarkhoksen näkemys avioliitosta näkyy selvimmin hänen teoksessaan Neuvoja vastanaineille. Myös muista Plutarkhoksen teoksista löytyy mainintoja avioliitosta ja puolisoiden rooleista. Uuden testamentin maininnat avioliitosta jakautuvat useisiin eri teksteihin. Evankeliumit käsittelevät avioeroa. Paavali käsittelee avioliittoa yleensä ja seksuaalisuutta avioliitossa. Uuden testamentin myöhemmät kirjeet, varsinkin niiden huoneentaulut, ja apostolisten isien tekstit keskittyvät eniten puolisoiden rooleihin avioliitossa. Plutarkhoksen näkemys avioliitosta oli positiivinen. Tämä näkyy useissa hänen teoksistaan. Kristittyjen kirjoittajien näkemys avioliitosta ei ole niin yksiselitteisen positiivinen. Paavali ei perustele avioliittoa muuten kuin haureuden välttämisellä. Kuitenkin Efesolaiskirjeessä avioliitto käy metaforaksi Kristuksen ja kirkon suhteelle. Plutarkhos ja kristityt kirjoittajat eivät anna paljon ohjeita puolison valinnasta. Plutarkhoksen mukaan puolison valinnassa tulee katsoa hänen luonnettaan, ei varallisuutta tai ulkonäköä. Paavalin ja Ignatioksen mukaan on parempi, jos puoliso on myös kristitty. Kristityt antavat myös ohjeita seka-avioliittoon, jossa puoliso on ei-uskova. 1. Pietarin kirjeen mukaan vaimon tulee pysyä uskossaan, eikä pelätä miestään. Plutarkhoksen mukaan vaimon tulisi palvoa samoja jumalia kuin miehensäkin. Plutarkhos näyttää suhtautuvan naisten aloitteentekoon avioerossa kielteisemmin kuin miesten. Kristityt kirjoittajat suhtautuvat avioeroon kielteisesti, vaikka lieventävätkin Jeesuksen avioerokieltoa. Plutarkhos ei hyväksy miehen aviollista uskottomuutta, mutta antaa miehelle kuitenkin myönnytyksen, jos tämä on liian heikko kontrolloimaan itseään. Kristityt kirjoittajat suhtautuvat uskottomuuteen yksiselitteisen kielteisesti. Ohjeissa avioparille Plutarkhos korostaa avioliiton harmoniaa ja avioparin riitelemättömyyttä enemmän kuin kristityt kirjoittajat. Plutarkhoksen ja kristittyjen kirjoittajien ohjeet vaimolle ovat samanlaisia. Vaimon ihanteelliset ominaisuudet olivat samoja; naisen tuli olla siveellinen ja häveliäs sekä hiljainen. Sekä Plutarkhos että huoneentaulujen kirjoittajat olivat sitä mieltä, että naisen tulisi alistua miehelleen. Plutarkhos ei perustele alistumista mitenkään, kun taas kristityt kirjoittajat antavat aina jonkun perustelun. Yleisin perustelu on apologeettiset syyt. Myös miehelle annettavat ohjeet ovat samanlaiset. Miehen tulee hallita vaimoaan, mutta sekä Plutarkhos että kristityt kirjoittajat rajoittavat miehen hallintavaltaa. Mies toimii myös vaimonsa opettajana. Plutarkhos antaa enemmän ja yksityiskohtaisempia ohjeita seksistä kuin kristityt kirjoittajat. Kristityistä kirjoittajista ainoastaan Paavali paneutuu näihin kysymyksiin tarkemmin. Sekä Plutarkhoksen että Paavalin mukaan ihmisten piti suhtautua seksiin kunnioituksella ja välttää liiallista himoa.

"Mikä on meidän taistelurintamamme?" : Yhdysvaltojen mustien kansalaisoikeusliike Suomen kirkollisessa lehdistössä vuosina 1963–1968

Tutkin pro gradu -työssäni Yhdysvaltojen mustien kansalaisoikeusliikkeen käsittelyä Suomen kirkollisessa lehdistössä liikkeen keskeisimpinä toiminnan vuosina 1963–1968. Selvitän, miten kirkollinen lehdistö reagoi kansalaisoikeusliikkeeseen, ja mitkä olivat niitä asioita ja tapahtumia, joita lehdet toivat liikkeestä esille. Keskeistä työssäni on myös kansalaisoikeusliikkeen näkyvimmän johtajan Martin Luther King Juniorin lehdistössä saaman huomion analysointi. Olennaista tutkimuksen kannalta on selvittää, käsittelivätkö tutkimani lehdet kansalaisoikeusliikkeen toimintaa hengellisestä näkökulmasta vai pelkästään uutisina Yhdysvaltojen poliittisista tapahtumista. Käytännössä tähän liittyy myös kysymys siitä, koskettiko Yhdysvaltojen mustien ahdinko kirjoitusten mukaan suomalaista kristittyä. Tutkimukseni taustan kannalta tärkeää on selvittää mustien rotusorron historiaa Yhdysvalloissa sekä Kingin liikkeeseen tuomaa ajattelupohjaa. Tutkimukseni lähteinä käytän Kotimaan, Församlingsbladetin, Herättäjän, Sanan ja Etsijän numeroita vuosilta 1963–1968. Vuodelta 1967 lähdemateriaalia ei ole kuitenkaan löytynyt. Ajallisesti tutkimus sijoittuu kansalaisoikeusliikkeen organisoiman Birminghamin kampanjan alusta aina Kingin murhan aiheuttamaan kuohuntaan asti. Tutkimukseni on vahvasti sidottu kansalaisoikeusliikkeen keskeisiin tapahtumiin, joiden kautta esittelen liikkeen saamaa huomiota. Tämän takia en käykään, Etsijää lukuun ottamatta, järjestelmällisesti läpi kaikkia tutkimieni vuosien numeroita, vaan tutkittavat numerot ovat ilmestyneet aikoina, jolloin kansalaisoikeusliike toimi aktiivisesti ja näkyvästi. Tutkimukseni on kirkollisen lehdistön ja kansalaisoikeusliikkeen tutkimuksessa ainutlaatuinen. Liikkeen lehdistössä saamaa vastaanottoa ei ole Suomessa aiemmin tutkittu. Kansalaisoikeusliikettä koskeva tutkimus on keskittynyt lähinnä Kingin ajattelun kuvailuun. Merkityksellisen tutkimusaiheesta tekee myös se, että syvemmällä tasolla tutkimus kuvailee sitä, millaisena kirkon epäviralliset äänenkannattajat näkivät ajan, jolloin yhteiskunnan sosiaalisiin ongelmiin puuttuminen alettiin nähdä kristityn tehtävänä. Lehtien kansalaisoikeusliikkettä koskeva keskustelu onkin nähtävä osana muuta ajan kehitystä ja sen henkeä. Vuosikymmenen ajan henki ja aikakauden suuret muutokset näkyvät selkeästi tutkimukseni tuloksissa. Kaukaisesta tapahtumapaikastaan huolimatta Yhdysvaltojen mustien kansalaisoikeusliike sai varsin paljon huomiota tutkimissani lehdissä niin pakinoissa, uutisissa kuin raporteissa tapahtumapaikoiltakin. Liikkeen toimintaa ja erityisesti Kingiä liikkeen johtajana ihailtiin ja liikettä hyödynnettiin esimerkkinä siitä, miten suomalaisten kristittyjenkin tulisi suhtautua maailmaan. Useissa lehdissä koettiinkin tarpeelliseksi nostaa esille Suomen omia ”rotukysymyksiä”, joista keskeisimpänä nähtiin romanien asema. Ajan kehitykseen varauksellisesti suhtautuvaa Herättäjää lukuun ottamatta lehdet suhtautuivat hyvin suopeasti mustien kansalaisoikeusliikkeen tarjoamaan sosiaalisen herätykseen. Erityisesti Kotimaan päätoimittaja Simo Talvitie paneutui mustien rotusortoon ja sen tarjoamiin opetuksiin myös Suomen tasolla. Selityksenä lehtien mustien kansalaisoikeusliikkeen runsaalle käsittelylle ja niiden tavalle käsitellä liikettä nousee keskeisenä aikaa leimaava kansainvälistyminen. Median kehittyminen erityisesti television myötä ja matkustamisen helpottuminen mahdollistivat entistä enemmän muiden maiden tapahtumien seuraamisen ja niihin kantaa ottamisen. Aikaansa seuraavien kristittyjen tehtäväksi nähtiinkin maailman tapahtumista perillä oleminen ja myös oman yhteiskunnan epäkohtien esille tuominen. Nämä eivät tutkimukseni mukaan olleet vain radikaalin ylioppilasnuorison kiinnostuksen kohteita vaan vähitellen myös monen suomalaisen kristityn.

Venäjän politiikka ja perustuslaki : Tutkimus Venäjän perustuslakikäsitteistön kehityksestä 1900-luvulla

Constitutional politics in Russia, a conceptual history study of the constitutional rhetoric in the 20th century In April 2006 the Russian Constitution had its 100th anniversary. Following its late start, five constitutions have been adopted. The great number of constitutions is partly explained in my work by the fact that Russia s political system has changed many times, from one state system to another. From a monarchical state power, it changed first, with the October revolution, into the Russian Socialist Federal Soviet Republic, and after that, in 1924, into the Union of Soviet Socialist Republics. In 1991, the Russian Federation was established. The great number of constitutions can also be explained by the fact that in a one-party system, constitutional concepts became one of the most important instruments for introducing political programmes. When the political unity of the state was not only restricted by the Constitution, but also by the party ideology, the political debates concerning constitutional concepts were the key discussions for all the reformative pursuits of Soviet politics. It can be said that, in the Soviet Union, almost all political discourses dealt with constitutional concepts. In the context of restricted unity, the constitutional concepts were the most important tools to argue and create a basis for a new presentation and new political programmes. Thus, the basic feature of the Soviet political discourses has been a continuous competition regarding the constitutional concepts. By defining the constitutional concepts, a new, the political elites wanted especially to redefine, their own way, the traditional meanings of the October 1917 Revolution, and to differentiate them from those of the preceding period of power. From a methodological point of view, I argue that the Russian constitutional concepts make a conceptual historical approach very suitable, and change the focus on history. This approach studies history in contemporary contexts which follow after each other, and whose texts are the main research target. The picture of history is created through the interpretation of the original sources of contemporary contexts. Focusing on the dynamic and traditional characteristic of Russian constitutional concepts, I refer to a certain kind of value and the task of these concepts to justify and define the political and societal unity in every situation. This is done by combining the pursued future orientation of constitutional unity with the new acts of preservation of the traditional principles of the revolution. The different time layers of the constitutional concepts, the past, the present and the future, are the key aspects of storytelling in justifying the continuity and redefining the constitutional unity for the sake of reform. These aspects of constitutional concepts, in addition to all the other functions, have been the main elements of the argumentative structure of acting against opponents.