Antiretroviral agents and acid-base balance at delivery of the neonate

Limited evidence is available regarding antiretroviral (ARV) safety for uninfected infants exposed to these drugs in utero. Our objective was to determine if ARV administered to pregnant women is associated with decreasing umbilical arterial pH and base excess in uninfected infants. A prospective study was conducted on 57 neonates divided into three groups: ZDV group, born to mothers taking zidovudine (N = 20), triple therapy (TT) group, born to mothers taking zidovudine + lamivudine + nelfinavir (N = 25), and control group (N = 12), born to uninfected mothers. Umbilical cord blood was used to determine umbilical artery gases. A test was performed to calculate the sample by comparing means by the unpaired one-tailed t-test, with a = 0.05 and ß = 20%, indicating the need for a sample of 18 newborn infants for the study groups to detect differences higher than 20%. The control and ARV groups were similar in gestational age, birth weight, and Apgar scores. Values of pH, pCO2, bicarbonate, and base excess in cord arterial blood obtained at delivery from the newborns exposed to TT were 7.23, 43.2 mmHg, 19.5 mEq/L, and -8.5 nmol/L, respectively, with no significant difference compared to the control and ZDV groups. We conclude that intrauterine exposure to ARV is not associated with a pathological decrease in umbilical arterial pH or base excess. While our data are reassuring, follow-up is still limited and needs to be continued into adulthood because of the possible potential for adverse effects of triple antiretroviral agents.

Animal model for age- and sex-related genotoxicity of diethylstilbestrol

Environmental xenoestrogens pose a significant health risk for all living organisms. There is growing evidence concerning the different susceptibility to xenoestrogens of developing and adult organisms, but little is known about their genotoxicity in pre-pubertal mammals. In the present study, we developed an animal model to test the sex- and age-specific genotoxicity of the synthetic estrogen diethylstilbestrol (DES) on the reticulocytes of 3-week-old pre-pubertal and 12-week-old adult BALB/CJ mice using the in vivo micronucleus (MN) assay. DES was administered intraperitoneally at doses of 0.05, 0.5, and 5 µg/kg for 3 days and animals were sampled 48, 72 and 96 h, and 2 weeks after exposure. Five animals were analyzed for each dose, sex, and age group. After the DES dose of 0.05 µg/kg, pre-pubertal mice showed a significant increase in MN frequency (P < 0.001), while adults continued to show reference values (5.3 vs 1.0 MN/1000 reticulocytes). At doses of 0.5 and 5 µg/kg, MN frequency significantly increased in both age groups. In pre-pubertal male animals, MN frequency remained above reference values for 2 weeks after exposure. Our animal model for pre-pubertal genotoxicity assessment using the in vivo MN assay proved to be sensitive enough to distinguish age and sex differences in genome damage caused by DES. This synthetic estrogen was found to be more genotoxic in pre-pubertal mice, males in particular. Our results are relevant for future investigations and the preparation of legislation for drugs and environmentally emitted agents, which should incorporate specific age and gender susceptibility.

The chronic blockade of angiotensin I-converting enzyme eliminates the sex differences of serum cytokine levels of spontaneously hypertensive rats

Sex hormones modulate the action of both cytokines and the renin-angiotensin system. However, the effects of angiotensin I-converting enzyme (ACE) on the proinflammatory and anti-inflammatory cytokine levels in male and female spontaneously hypertensive rats (SHR) are unclear. We determined the relationship between ACE activity, cytokine levels and sex differences in SHR. Female (F) and male (M) SHR were divided into 4 experimental groups each (n = 7): sham + vehicle (SV), sham + enalapril (10 mg/kg body weight by gavage), castrated + vehicle, and castrated + enalapril. Treatment began 21 days after castration and continued for 30 days. Serum cytokine levels (ELISA) and ACE activity (fluorimetry) were measured. Male rats exhibited a higher serum ACE activity than female rats. Castration reduced serum ACE in males but did not affect it in females. Enalapril reduced serum ACE in all groups. IL-10 (FSV = 16.4 ± 1.1 pg/mL; MSV = 12.8 ± 1.2 pg/mL), TNF-α (FSV = 16.6 ± 1.2 pg/mL; MSV = 12.8 ± 1 pg/mL) and IL-6 (FSV = 10.3 ± 0.2 pg/mL; MSV = 7.2 ± 0.2 pg/mL) levels were higher in females than in males. Ovariectomy reduced all cytokine levels and orchiectomy reduced IL-6 but increased IL-10 concentrations in males. Castration eliminated the differences in all inflammatory cytokine levels (IL-6 and TNF-α) between males and females. Enalapril increased IL-10 in all groups and reduced IL-6 in SV rats. In conclusion, serum ACE inhibition by enalapril eliminated the sexual dimorphisms of cytokine levels in SV animals, which suggests that enalapril exerts systemic anti-inflammatory and anti-hypertensive effects.

Effect of hyperbaric oxygenation on mitochondrial function of neuronal cells in the cortex of neonatal rats after hypoxic-ischemic brain damage

The timing and mechanisms of protection by hyperbaric oxygenation (HBO) in hypoxic-ischemic brain damage (HIBD) have only been partially elucidated. We monitored the effect of HBO on the mitochondrial function of neuronal cells in the cerebral cortex of neonatal rats after HIBD. Neonatal Sprague-Dawley rats (total of 360 of both genders) were randomly divided into normal control, HIBD, and HIBD+HBO groups. The HBO treatment began immediately after hypoxia-ischemia (HI) and continued once a day for 7 consecutive days. Animals were euthanized 0, 2, 4, 6, and 12 h post-HI to monitor the changes in mitochondrial membrane potential (ΔΨm) occurring soon after a single dose of HBO treatment, as well as 2, 3, 4, 5, 6, and 7 days post-HI to study ΔΨm changes after a series of HBO treatments. Fluctuations in ΔΨm were observed in the ipsilateral cortex in both HIBD and HIBD+HBO groups. Within 2 to 12 h after HI insult, the ΔΨm of the HIBD and HIBD+HBO groups recovered to some extent. A secondary drop in ΔΨm was observed in both groups during the 1-4 days post-HI period, but was more severe in the HIBD+HBO group. There was a secondary recovery of ΔΨm observed in the HIBD+HBO group, but not in the HIBD group, during the 5-7 days period after HI insult. HBO therapy may not lead to improvement of neural cell mitochondrial function in the cerebral cortex in the early stage post-HI, but may improve it in the sub-acute stage post-HI.

Form, size and volumetric expansion of Adzuki beans (Vigna angularis) during soaking

This study analyzed the variation in shape and size of Adzuki beans during soaking at different temperatures. In addition, different mathematical models were fitted to the experimental values of volumetric expansion, selecting the best one. Grains of Adzuki beans (Vigna angularis) with moisture content of approximately 0.25 (decimal d.b.) were manually harvested; they were, then, dried to 0.128 (decimal d.b.). The beans were subjected to soaking in distilled water at the temperatures 18 ± 1, 27 ± 1, 36 ± 1, and 45 ± 1 °C, in five repetitions. Recipients containing 80 mL of distilled water and 20 g of beans for each sample were used. The samples were periodically weighed in order to determine the water absorption. After that, the samples were removed from the recipients and placed on filter papers for two minutes to drain the surface water. Water absorption continued until the beans reached the saturation moisture content. It was concluded that, the form of the Adzuki beans was altered regularly, the orthogonal axes expanded differentially in the radial and axial directions, and that the linear model appropriately described the volumetric expansion of the Adzuki beans, among the series of models analyzed for the temperatures 18, 27, 36 and 45 °C.

Ripening pattern of guava cv. Pedro Sato

Guava is a fruit with high respiration rates and a very short shelf life. Since information on its respiration pattern is contradictory, the objective was to study the changes occurring in the fruit during ripening and to relate them to the respiration behavior of this fruit. Guavas were picked at the half-ripe stage and stored for 8 days at 22 ± 1 ºC and 78 ± 1% relative humidity. The analyses conducted were: peel and pulp coloration, firmness, total soluble solids (TSS), total titratable acidity (TTA), and ethylene production. According to the results, it was verified that the parameters analyzed apparently do not coincide and are ethylene-independent. There was an accentuated ethylene production during ripening, starting from the 4th day. The ethylene synthesis continued increasing up to the 8th day, when the fruits were already decomposing. It was observed that the firmness decreased sharply in the first three days of ripening, and the skin and pulp color changed during ripening. The TSS, total soluble solids, and the TTA, total titratable acidity, practically did not change during the ripening, even with the increased ethylene production. It can be concluded that guava is a fruit that presents characteristics of climacteric and non-climacteric fruits.

Formal modelling for digital media distribution

Human beings have always strived to preserve their memories and spread their ideas. In the beginning this was always done through human interpretations, such as telling stories and creating sculptures. Later, technological progress made it possible to create a recording of a phenomenon; first as an analogue recording onto a physical object, and later digitally, as a sequence of bits to be interpreted by a computer. By the end of the 20th century technological advances had made it feasible to distribute media content over a computer network instead of on physical objects, thus enabling the concept of digital media distribution. Many digital media distribution systems already exist, and their continued, and in many cases increasing, usage is an indicator for the high interest in their future enhancements and enriching. By looking at these digital media distribution systems, we have identified three main areas of possible improvement: network structure and coordination, transport of content over the network, and the encoding used for the content. In this thesis, our aim is to show that improvements in performance, efficiency and availability can be done in conjunction with improvements in software quality and reliability through the use of formal methods: mathematical approaches to reasoning about software so that we can prove its correctness, together with the desirable properties. We envision a complete media distribution system based on a distributed architecture, such as peer-to-peer networking, in which different parts of the system have been formally modelled and verified. Starting with the network itself, we show how it can be formally constructed and modularised in the Event-B formalism, such that we can separate the modelling of one node from the modelling of the network itself. We also show how the piece selection algorithm in the BitTorrent peer-to-peer transfer protocol can be adapted for on-demand media streaming, and how this can be modelled in Event-B. Furthermore, we show how modelling one peer in Event-B can give results similar to simulating an entire network of peers. Going further, we introduce a formal specification language for content transfer algorithms, and show that having such a language can make these algorithms easier to understand. We also show how generating Event-B code from this language can result in less complexity compared to creating the models from written specifications. We also consider the decoding part of a media distribution system by showing how video decoding can be done in parallel. This is based on formally defined dependencies between frames and blocks in a video sequence; we have shown that also this step can be performed in a way that is mathematically proven correct. Our modelling and proving in this thesis is, in its majority, tool-based. This provides a demonstration of the advance of formal methods as well as their increased reliability, and thus, advocates for their more wide-spread usage in the future.

Urana työllistyminen

Tutkimuksen tarkoituksena on ollut selvittää pitkään työttömänä olleiden ammatinvaihtajien ammatinvaihdon ja työllistymisen etenemistä. Tämän lisäksi tutkimuksessa on tarkasteltu kohderyhmän mielikuvaa ohjaavasta koulutuksesta. Pitkittäistutkimus on toteutettu seurannalla, jonka välietappina on ollut kohderyhmän osallistuminen ohjaavaan koulutukseen. Työvoimapoliittinen ohjaava koulutus edusti erityisesti vaikeasti työllistettäville kohdistettavaa interventiota, jolla pyrittiin puuttumaan työttömyyskierteeseen ja ehkäisemään syrjäytymiskehityksen jatkuminen. Tutkimuksen kohderyhmäksi valitut ihmiset (51) ovat suoranaisessa keskiössä tutkittaessa työelämästä syrjäytymistä. Heikentyneet työelämävalmiudet ja työmarkkinakelpoisuus ovat tehneet heistä vaikeasti työllistettäviä. Heidän valintansa kohderyhmäksi, työhallinnon tekemän kurssiosoituksen kriteereinä olevien pitkäaikaistyöttömyyden sekä epäonnistuneen ammatinvaihdon perusteella, osoittaa heidän olevan erityisen ohjauksen ja tuen tarpeessa. On kuitenkin huomattava, että heidät on valittu kohderyhmäksi paitsi kurssiosoituksen saaneina pitkäaikaistyöttöminä myös ammatinvaihtajina, jotka itse haluavat vaihtaa ammattiaan. Tutkimusaineistona ovat olleet työhallinnon asiakasrekisteritiedot ja seurantatutkimuksen perusteella muodostetuista ryhmistä valittujen neljän tapaushenkilön teemahaastatteluaineistot. Tutkimusaineistoa on käsitelty laadullisesti, koska tutkimus kuuluu laadullisen tutkimuksen piiriin sekä tutkimuksen kohteena olevan ilmiön, tutkimuskysymysten ja -aineistojen että tarkoituksensa perusteella. Tutkimuksessa on kuvattu pitkäaikaistyöttömien henkilöiden ammatinvaihtoa ja työllistymistä. Kuvatuissa tapauksissa ammatinvaihtotarve perustuu suurimmalla osalla terveydellisiin rajoitteisiin, joiden vuoksi aikaisemmassa työssä toimiminen on mahdotonta. Useimmiten vajaakuntoisuus on merkittävästi pitkittänyt heidän työttömyyttään. Tämän vuoksi seurantatutkimuksessa on keskitytty tarkastelemaan ammatinvaihtoprosessin etenemistä. Muun muassa työttömyyttä laajasti tutkineet Aho ja Vähätalo ovat todenneet vajaakuntoisuuden olevan merkittävä työttömyyden pitkittymiseen vaikuttava tekijä. Ahon mukaan vajaakuntoisiksi diagnosoituja on jopa viidennes kroonisesti pitkäaikaistyöttömistä työhallinnon asiakasrekisteriin kirjatuista henkilöistä. Monen tekijän summana pitkään työttömänä olleet henkilöt ovat vaarassa ajautua tilanteeseen, jossa he eivät enää kykene omin avuin löytämään ulospääsyä työttömyydestä Tämän seurantatutkimuksen perusteella vain hyvin harvalla kohderyhmään kuuluvista on ammatinvaihdossa ja työllistymisessä tapahtunut merkittävää edistymistä huolimatta useiden vuosien yrittämisestä. Ammatinvaihdon ja työllistymisen edistymistä on tarkasteltu sen perusteella, miten työelämään ja/tai koulutukseen sijoittumiset tai muut toiminnot ovat edesauttaneet tavoitteen toteutumista. Seurantatutkimuksessa on muodostettu neljä tyyppiryhmää ammatinvaihdon ja työllistymisen etenemisen perusteella. Ryhmät ovat: Ammatinvaihdossa onnistuneet (5), ammatinvaihdossa edistyneet (19), pitkäaikaistyöttömäksi jääneet (12) ja epätarkoituksenmukaisesti sijoittuneet (15). Ammatinvaihdossa onnistuneet ovat toteuttaneet ammatinvaihtonsa siirtymällä suoraan työelämään uudelle alalle, työllistymällä koulutusta vastaavaan työhön uudelleenkoulutuksen jälkeen tai kouluttautumalla uuteen ammattiin työllistymättä. Kuitenkin vain kolme heistä on sijoittunut seurannan päättyessä pysyväisluonteiseen terveydelleen soveltuvaan työhön muiden ollessa edelleen työttömänä. Ammatinvaihdossa edistyneet ovat suurimmaksi osaksi edistyneet ammatinvaihdossaan soveltuvien tukitöiden avulla. Työttömyys on kuitenkin jatkunut valtaosalla ja vain yksi heistä on sijoittuneena työelämään seurannan päättyessä. Tämä sijoittuminen ei ole kuitenkaan edistänyt ammatinvaihtoa. Pitkäaikaistyöttömäksi jääneet ovat olleet yhtäjaksoisesti työttömänä kokoseurantajakson ajan. Epätarkoituksenmukaisesti sijoittuneet ovat enimmäkseen sijoittuneet terveytensä kannalta haitallisiin ja/tai ammatinvaihtosuunnitelmilleen soveltumattomiin sijoitustöihin ja määräaikaisuuksiin. Seurannan päättyessä heovat joko työttömänä tai toimivat ammatinvaihtotavoitteensa kannalta haitallisissa työtehtävissä. Tämä on vahvistanut mielikuvaa, joka usealle heille on muodostunut ohjaavasta koulutuksesta työttömille suunnattuna sanktiona, joka ei edistä työllistymistä. Ohjaavassa koulutuksessa suurin osa heistä on kokenut hyötyneensä työharjoittelujaksosta, joka on antanut käyttökelpoista tietoa ammatinvalintaa varten. Lukuun ottamatta kolmea henkilöä, jotka ovat seurannan päättyessä pysyväisluonteisessa työssä terveydelleen soveltuvassa ammatissa, ovat kaikki muut kohderyhmään kuuluvat edelleen erityisen ohjauksen ja tuen tarpeessa johtuen ammatinvaihdon keskeneräisyydestä ja/tai työttömyyden jatkumisesta. Yhdistävänä tekijänä ammatinvaihdossa onnistuneilla vaikuttaa olleen tulevaisuususkon säilyminen pitkäaikaistyöttömyydessä. Sekä ammatinvaihdossa onnistuneet että edistyneet ovat kokeneet työttömyyteen katkoksia tuoneet työt merkityksellisinä riippumatta siitä, ovatko työtehtävät edistäneet ammatinvaihtoa.

Sähkönmyyntiyhtiöiden riskienhallinnan haasteet ja kehittäminen

Diplomityön tavoitteena on esitellä sähkökaupan ja erityisesti sähköyhtiöiden kokemia sähkönmyynnin riskejä sekä kuvata sähkönmyyntiin liittyvää riskienhallinnan problematiikkaa. Tarkastelun näkökulmana on tietojärjestelmien ja saatavissa olevan tiedon hyödyntäminen energiayhtiöiden riskienhallinnassa. Toinen päätavoitteista on tutkia, kuinka saatavilla olevaa tiedon hyödyntämistä voidaan kehittää sähkönmyynnin hinnoittelussa sekä suojausten suunnittelussa. Työ toteutettiin työskentelemällä asiantuntijana energia-alaan keskittyneessä ohjelmistoyrityksessä sekä haastattelemalla yhdeksän suomalaisen sähkönmyyntiyhtiön henkilöitä riskienhallinnan haasteiden sekä tietojärjestelmien näkökulmasta. Saatavilla olevien tietojen nykyistä parempi hyödyntäminen ja automatisointi voivat auttaa pienentämään yhtiöiden riskitasoa ja parantaa menestymisen edellytyksiä sähkönmyynnin vähittäismarkkinoilla. Lisäksi kulloiseenkin markkinatilanteeseen sopivat sähkön hankintahinnan suojausstrategiat sekä monipuoliset dynaamiset hinnoittelumallit auttavat pienentämään yhtiön kokemia riskejä tai niiden vaikutuksia. Näiden hyödyntäminen vaatii laajaa ymmärrystä sähkö- ja johdannaismarkkinoiden toiminnasta sekä usein myös nykyisten tietojärjestelmien kehittämistä. Tulevaisuudessa yhä yleistyvä hajautettu tuotanto sekä kysynnän jousto asettavat tietojärjestelmille uusia vaatimuksia, jotka toteutuessaan mahdollistavat uudenlaisten palveluiden käyttöönoton sekä voivat tuoda tilaa myös alan uusille toimijoille. Työssä käsitellään energiayhtiöiden kokemia riskejä sähkönmyynnin näkökulmasta, esitellään alan yleisimmät riskit sekä keinot ja työkalut niiltä suojautumiseen. Työn lopuksi tarkastellaan sähkönmyynnin ja –hankinnan oleellisimpia prosesseja riskienhallinnan kehittämisen näkökulmasta.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Clinical and genetic markers in disease progression – a study among subjects with obstructive lung diseases

Asthma, COPD, and asthma and COPD overlap syndrome (ACOS) are chronic pulmonary diseases with an obstructive component. In COPD, the obstruction is irreversible and the disease is progressive. The aim of the study was to define and analyze factors that affected disease progression and patients’ well-being, prognosis and mortality in Chronic Airway Disease (CAD) cohort. The main focus was on COPD and ACOS patients. Retrospective data from medical records was combined with genetic and prospective follow-up data. Smoking is the biggest risk factor for COPD and even after the diagnosis of the disease, smoking plays an important role in disease development and patient’s prognosis. Sixty percent of the COPD patients had succeeded in smoking cessation. Patients who had managed to quit smoking had lower mortality rates and less psychiatric diseases and alcohol abuse although they were older and had more cardiovascular diseases than patients who continued smoking. Genetic polymorphism rs1051730 in the nicotinic acethylcholine receptor gene (CHRNA3/5) associated with heavy smoking, cancer prevalence and mortality in two Finnish independent cohorts consisting of COPD patients and male smokers. Challenges in smoking cessation and higher mortality rates may be partly due to individual patient’s genetic composition. Approximately 50% of COPD patients are physically inactive and the proportion was higher among current smokers. Physically active and inactive patients didn’t differ from each other in regard to age, gender or comorbidities. Bronchial obstruction explained inactivity only in severe disease. Subjective sensation of dyspnea, however, had very strong association to inactivity and was also associated to low health related quality of life (HRQoL). ACOS patients had a significantly lower HRQoL than either the patients with asthma or with COPD even though they were younger than COPD patients, had better lung functions and smaller tobacco exposure.

Narratives of emergence: rising powers and the end of the Third World?

This article examines recent arguments from development economists, from historians and from international relations specialists that do challenge the continued relevance of the idea of the Third World. It then examines five reasons why these arguments are wrong. We can indeed understand much about emerging powers in terms of how they are seeking to navigate and best position themselves within an existing state-centric, liberal and capitalist order whilst accepting many of the underlying assumptions and values of that order. But the nature of that navigation has been shaped by their historical trajectory and by the developmental, societal and geopolitical context of their emergence.

Sellumassan varastosäiliön rakenneanalyysi

Tämä työ käsittelee valkaistun ja valkaisemattoman sellumassan varastosäiliön tärinää ja värähtelyä. Värähtelyn seurauksena säiliön seinämän jäykisterenkaan hitsausliitokseen on syntynyt särö. Työn tavoitteena on selvittää, mikä johtaa särön syntyyn ja miten kestäväm-piä varastosäiliöitä voidaan rakentaa materiaali-, valmistus- tai rakennemuutoksien avulla. Työ alkoi tutkimalla rakennemateriaalina olevan duplex-teräksen mikrorakenteen ominai-suuksia, sekä sen hitsattavuutta ja seostamista kirjallisuustutkimuksena. Kirjallisuustutki-musta jatkettiin selvittämällä mahdollisia vaurion syntymekanismeja seinämän särölle. Työssä analysoitiin myös tehtaalla mitattuja värähtelyarvoja. Lopuksi laskettiin FE-analyysillä tyhjän varastosäiliön ominaismuodot ja -taajuudet moodianalyysillä, sekä selvi-tettiin harmonisella analyysillä pinnankorkeuden vaihtelun vaikutus siirtymävasteeseen ja kriittisiin värähtelytaajuuksiin. Varastosäiliöön kohdistuvaa värähtelyä ei ole mahdollista poistaa kokonaan, mutta väräh-telyn aiheuttamia seurauksia kyetään rajaamaan useilla keinoilla. Toimenpiteinä voivat olla ainakin seinämän materiaalin paksuuden lisääminen, jäykisteripojen lisääminen ja kriittisten sellun pinnankorkeuksien välttäminen. Kriittiseksi pinnankorkeudeksi havaittiin 40–45 %:n täyttöaste ja turvalliseksi korkeudeksi 35–38 %:n täyttöaste. Varastosäiliölle kriittisen ominaistaajuuden katsotaan syntyvän taajuuksilla 3,3–3,8 Hz ja 5,8–6,4 Hz. Sellumassa putoaa varastosäiliöön noin 2 Hz taajuudella.

Viologen based electroactive polymers and composites for durable electrochromic systems

Electrochromism, the phenomenon of reversible color change induced by a small electric charge, forms the basis for operation of several devices including mirrors, displays and smart windows. Although, the history of electrochromism dates back to the 19th century, only the last quarter of the 20th century has its considerable scientific and technological impact. The commercial applications of electrochromics (ECs) are rather limited, besides top selling EC anti-glare mirrors by Gentex Corporation and airplane windows by Boeing, which made a huge commercial success and exposed the potential of EC materials for future glass industry. It is evident from their patents that viologens (salts of 4,4ʹ-bipyridilium) were the major active EC component for most of these marketed devices, signifying the motivation of this thesis focusing on EC viologens. Among the family of electrochromes, viologens have been utilized in electrochromic devices (ECDs) for a while, due to its intensely colored radical cation formation induced by applying a small cathodic potential. Viologens can be synthesized as oligomer or in the polymeric form or as functionality to conjugated polymers. In this thesis, polyviologens (PVs) were synthesized starting from cyanopyridinium (CNP) based monomer precursors. Reductive coupling of cross-connected cyano groups yields viologen and polyviologen under successive electropolymerization using for example the cyclic voltammetry (CV) technique. For further development, a polyviologen-graphene composite system was fabricated, focusing at the stability of the PV electrochrome without sacrificing its excellent EC properties. High electrical conductivity, high surface area offered by graphene sheets together with its non-covalent interactions and synergism with PV significantly improved the electrochrome durability in the composite matrix. The work thereby continued in developing a CNP functionalized thiophene derivative and its copolymer for possible utilization of viologen in the copolymer blend. Furthermore, the viologen functionalized thiophene derivative was synthesized and electropolymerized in order to explore enhancement in the EC contrast and overall EC performance. The findings suggest that such electroactive viologen/polyviologen systems and their nanostructured composite films as well as viologen functionalized conjugated polymers, can be potentially applied as an active EC material in future ECDs aiming at durable device performances.

Interactions of decision mechanisms in an entrepreneurial firm’s journey to become a major player in its industry

This study discusses the interactions of different decision-making mechanisms in the process of change of a successful entrepreneurial dairy firm in Vietnam. The purpose of the study is to construct a theoretical framework, which explains the interactions between effectual and causal decision-making processes in different phases of business, and to provide a real life example with practical recommendations for entrepreneurs and managers. In order to achieve this purpose, a preliminary theoretical framework was built, using process theories applied to different decision making modes, referred to as causation and effectuation. The case was studied through ethnographic research method, with three semi-structured interviews, one unstructured interview, secondary data and observations within four months in 2013-2014. After the data was analyzed, a modified framework was drawn from the result. The finding of this study shows that there was an interaction between effectual and causal decision-making processes in different stages of the company’s development. The entrepreneur applied effectual decision-making process to develop a unique business model and a new dairy market segment. However, when a new market demand arose, the company’s resources became insufficient, they thus had to shift to causation process to adapt to market change. Simultaneously, with better-accumulated resources, the entrepreneur continued the effectuation process to create another brand new dairy market segment. This study, thus, contributes to effectuation theory, emphasizing the necessity of combining effectual and causal decision-making processes in different phases of business. It is suggested that business would develop with an effectual process until a business model is viable for growth. It continues to use this process up to a certain degree. When the market changes, the company needs to collect more means to adapt to the changes. They need to set new goals and this is a shift to the use of causal process, which builds on prediction. It uses goals and teleology as driving mechanisms and tries to exploit and fill potential resource gaps to achieve these goals. At the same time, there are new iterations that look to establish new lines or types of business with the given means, which are now well established. This again employs effectual mechanisms, which are based on evolutionary process, until they reach the stage of viable tested business model. Moreover, this study hopes to provide know-how to entrepreneurs and managers of small companies in similar situations, suggesting how to combine effectual and causal decision-making processes to deal with various circumstances in different times.