Raakafosfaatin liuotus ja ammonointi

Apatiittien käyttöä raaka-aineena lannoitteiden valmistusprosessissa on usein hankaloittanut lannoitelietteen viskositeetin kasvu, kun hapanta lannoitelietettä on neutraloitu ammoniakilla. Työn tarkoituksena oli tutkia lannoitelietteen viskositeettiin vaikuttavia tekijöitä ja tekijöiden vaikutusta lannoitteen ominaisuuksiin. Työn kirjallisen osan alkupuoliskolla käsiteltiin raakafosfaatteja ja fosfaattilannoitteita. Tämän jälkeen keskityttiin lannoitteiden valmistukseen sekä viskositeetin merkitykseen lannoiteprosesseissa. Työn kokeellisessa osassa tutkittiin raakafosfaatin, liuotushapon, liuotushappomäärän, ammonointiajan sekä apatiitti/fosforihappo-suhteen vaikutusta lannoitteen ominaisuuksiin. Kokeet aloitettiin raakafosfaatin liuotuksella happoon. Tämän jälkeen liete neutraloitiin ammoniakilla ja suoritettiin muiden ravinteiden lisäys. Lannoitelietteen viskositeettiin voimakkaimmin vaikuttavat tekijät olivat kokeissa käytetty liuotushappo, ammonointiaika sekä raakafosfaatti. Raakafosfaatilla, liuotushapolla sekä apatiitti/fosforihappo-suhteella havaittiin olevan suurin merkitys lannoitteen fosforin vesiliukoisuudelle.

Japanin musiikkimarkkinat : Japanin pop- ja rock-markkinoiden erityispiirteet suomalaisen musiikin näkökulmasta

Tämän opinnäytetyön tavoite on selvittää suomalaisen pop- ja rock-musiikin vientimahdollisuuksia yhteen maailman kiinnostavimpaan ja ostovoimaisimpaan maahan, Japaniin, ja tuoda esille sen luonnetta suhteessa suomalaiseen musiikkiin. Opinnäytetyön teoriaosa selvittää Suomen tämän hetkistä musiikkiviennin tilannetta ja syitä siihen, miksi Japanin markkinat on erittäin kiinnostava alue viennin saralla. Kirjallinen viitekehys työlle muodostuu pääasiassa kootuista musiikkialan raporteista, tilastoista ja artikkeleista. Empiirisessä osassa keskeistä tutkimusmateriaalia ovat Tokion Suomen Instituutissa kolmen kuukauden työharjoittelun yhteydessä kertyneet kokemukset ja asiantuntijahaastatteluaineisto. Nämä avaavat Japanin musiikkimarkkinoita luoden parempaa kuvaa siellä vallitsevista kilpailuolosuhteista, maan tavoista ja kiinnostuksen kohteista, sekä japanilaisten mielikuvaa suomalaisesta musiikista. Suomessa musiikkimarkkinat ovat hyvin pienet, mutta niiden laajentamiseen viennillä on alettu keskittyä yhä enenevissä määrin. Koska Japanissa on maailman toiseksi suurimmat musiikkimarkkinat, se on erittäin varteenotettava kohde myös suomalaisen musiikin viennille. Vaikka suomalainen musiikki on toistaiseksi suhteellisen tuntematonta suurelle osalle japanilaisista, suhtaudutaan siihen positiivisesti. Japanilaisten mielestä Suomesta tuleva musiikki on verrattuna moniin muihin maihin paljon omaleimaisempaa ja tämä tekee siitä kiinnostavan. Viennissä ongelmia kuitenkin luovat kielimuuri ja japanilaisten kulttuurisidonnaiset toimintatavat. Ilman hyviä suhteita toiminta Japanin musiikkialan kentällä on lähes mahdotonta. Keskeistä on huomioida paikalliset toimintatavat ja toimia kiireettä kaukonäköisesti. Tuotteen kaikkien osa-alueiden tulisi olla suunniteltu Japanin markkinoihin soveltuviksi jo tarjontavaiheessa. Parantaakseen suomalaisen musiikin vientiä Japaniin on tärkeää tuotteiden menestyksien yhteydessä tuoda esille niiden suomalaisuutta ja näin lisätä kiinnostusta japanilaisten silmissä. Lähtökohtaisesti suomalaisella musiikilla on kuitenkin hyvät mahdollisuudet menestykseen Japanin musiikkimarkkinoilla. Suurimpina ongelmina voidaan pitää vähäistä tietoa japanilaisten mielenkiinnon kohteista, toimintatapojen kulttuurisia eroja ja suomalaisten vientiin panostettavien varojen vähyyttä.

Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

Reaching influential early adopters effectively in Finland : Rock Science – new generation board game

Innovations diffuse at different speed among the members of a social system through various communication channels. The group of early adopters can be seen as the most influential reference group for majority of people to base their innovation adoption decisions on. Thus, the early adopters can often accelerate the diffusion of innovations. The purpose of this research is to discover means of diffusion for an innovative product in Finnish market through the influential early adopters in respect to the characteristics of the case product. The purpose of the research can be achieved through the following sub objectives:  Who are the potential early adopters for the case product and why?  How the potential early adopters of the case product should be communicated with?  What would be the expectations, preferences, and experiences of the early adopters of the case product? The case product examined in this research is a new board game called Rock Science which is considered to be incremental innovation bringing board gaming and hard rock music together in a new way. The research was conducted in two different parts using both qualitative and quantitative research methods. This mixed method research began with expert interviews of six music industry experts. The information gathered from the interviews enabled researcher to compose the questionnaire for the quantitative part of the study. Internet survey that was sent out resulted with a sample of 97 responses from the targeted population. The key findings of the study suggest that (1) the potential early adopters for the case product are more likely to be young adults from the capital city area with great interest in rock music, (2) the early adopters can be reached effectively through credible online sources of information, and (3) the respondents overall product feedback is highly positive, except in the case of quality-price ratio of the product. This research indicates that more effective diffusion of Rock Science board game in Finland can be reached through (1) strategic alliances with music industry and media partnerships, (2) pricing adjustments, (3) use of supporting game formats, and (4) innovative use of various social media channels.

Rakennettu areenatähteys. Rock-konsertti globalisoituvana mediaspektaakkelina 1965-2013

Kulttuurihistorian alaan kuuluva artikkeliväitöskirja edustaa populaarikulttuurin ja tarkemmin populaarimusiikin tutkimusta kiinnittyen ennen muuta audiovisuaalisen mediakulttuurin muutokseen 1960-luvulta tähän päivään. Väitöskirja käsittelee Pink Floydin, The Rolling Stonesin, U2:n ja Peter Gabrielin areenakonserttikiertueita ja kyseisten kiertueiden lavasuunnittelijoiden Mark Fisherin ja Robert Lepagen toimintaa. Tutkimus tarkastelee, miten jättiläismäiset mediaspektaakkelit saivat alkunsa, ammattimaistuivat ja globalisoituivat vuosien 1965–2013 välillä. Analyysin kohteena on se, miten ne rakentuivat ja toisaalta rakensivat areenatähteyttä sekä uudistivat audiovisuaalista kulttuuria. Konserttien avainkohtia ja populaarijulkisia aineistoja hermeneuttisesti tulkiten ja lähilukien sekä historiallisesti kontekstoiden tutkimus rakentaa kulttuurihistoriallisen kokonaistulkinnan viihdeteollisuuden mahtipontiseksi muotoutuneen ilmiön tuotannosta. Tutkimuksen lähtökohtana on populaarimusiikkitähden vaikutus 1900-luvun jälkipuoliskon ja 2000-luvun alun massamediassa ja kulttuurissa. Tarkastelemalla areenarockin mediaspektaakkeleiden kulttuurihistoriaa tutkimus ottaa kantaa niihin kaupallisiin, teknologisiin ja poliittisiin muutoksiin, jotka ovat viimeisen viidenkymmenen vuoden aikana mahdollistaneet tähteyden globaalia leviämistä. Tämän muutoksen seurauksena lähes kenestä tahansa voi tulla tähti ja lähes mistä tahansa kulttuuri-ilmiöstä voi tulla populaaria. Mutta vain jotkut tähdet ja yhtyeet esiintyvät täysille areenoille. Areenakonsertit ovatkin tähteysilmiön keskeisiä huipentumia, globaalin viihdekulttuurin äärimmäisiä manifestaatioita. Nykyiset areenoilla tapahtuvat mediaspektaakkelit ovat monimutkaista audiovisuaalista musiikkiteatteria, jossa kaikkien esityksen elementtien – teatraalisten ja audiovisuaalisten efektien – tulee olla mahdollisimman suuria ja taitavasti rytmitettyjä. Mediaspektaakkelien analyysissa tulee erityisesti kohdistaa huomio erilaisten medioiden suhteisiin sekä kysymykseen siitä, miten suuri osa audiovisuaalista konserttikokemusta itse asiassa on ennalta rakennettua ja nauhoitettua. Lavasuunnittelu yhdistää esiintyjän teatraaliset eleet ja esiintymisen laajempaan audiovisuaaliseen ja ennalta mietittyyn temaattiseen kokonaisuuteen. Tähän kuuluvat suurten konserttilavojen kertakäyttöarkkitehtuuri, valon ja pintojen yhdistäminen populaariin kuvastoon sekä itse teoksien audiovisuaalisen kerronnan historiallisiin ja nostalgisiin viitteisiin.

Intensification of Operation of Inclined Plate Settler at Fertilizer Plant

Fertilizer plant’s process waters contain high concentrations of nitrogen compounds, such as ammonium and nitrate. Phosphorus and fluorine, which originate from phosphoric acid and rock phosphate (apatite) used in fertilizer production, are also present. Phosphorus and nitrogen are the primary nutrients causing eutrophication of surface waters. At fertilizer plant process waters are held in closed internal circulation. In a scrubber system process waters are used for washing exhaust gases from fertilizer reactors and dry gases from granulation drums as well as for cooling down the fertilizer slurry in neutralization reactor. Solids in process waters are separated in an inclined plate settler by gravitational sedimentation. However, the operation of inclined plate settler has been inadequate. The aim of this thesis was to intensify the operation of inclined plate settler and thus the solids separation e.g. through coagulation and/or flocculation process. Chemical precipitation was studied to reduce the amount of dissolved species in process waters. Specific interest was in precipitation of nitrogen, phosphorus, and fluorine containing specimens. Amounts of phosphorus and fluorine were reduced significantly by chemical precipitation. When compared to earlier studies, annual chemical costs were almost eight times lower. Instead, nitrogen compounds are readily dissolved in water, thus being difficult to remove by precipitation. Possible alternative techniques for nitrogen removal are adsorption, ion exchange, and reverse osmosis. Settling velocities of pH adjusted and flocculated process waters were sufficient for the operation of inclined plate settler. Design principles of inclined plate settler are also presented. In continuation studies, flow conditions in inclined plate settler should be modelled with computational fluid dynamics and suitability of adsorbents, ion exchange resins, and membranes should be studied in laboratory scale tests.

Sphingosine-1-phosphate-evoked invasion of follicular thyroid cancer cells : evidence for the involvement of HIF-Iα, MMP2 and MMP9

Sphingolipids are widely expressed molecules, which traditionally were considered to have majorly structural properties. Nowadays, however, they are implicated in a wide range of different biological processes. The bioactive lipid sphingosine 1-phosphate (S1P) has emerged during the past decade as one of the most studied molecules due to its proliferative and pro-migratory abilities both during normal physiology and in the pathology of a subset of different diseases. Migration and invasion of cancer cells require changes in cell behavior and modulation of the tissue microenvironment. Tumor aggressiveness is markedly enhanced by hypoxia, in which hypoxia inducible transcription factors 1-2α (HIF-1-2α) are activated to promote metabolism, proliferation and migration. Invasion requires degradation of the extracellular matrix (ECM) achieved by several degrading and remodeling enzymes. Matrix metalloproteinases (MMPs) are broadly expressed and well accepted as proteolytic enzymes with essential roles both in normal physiology and in pathology. Previously, S1P was shown to strongly evoke migration of follicular ML-1 thyroid cancer cells. The objective of this study was to further investigate and understand the mechanisms behind this regulation. In the first project it was demonstrated that S1P enhances the expression and activity of HIF-1α. S1P enhanced the expression of HIF-1α by increasing its synthesis and stability. The S1P-increased HIF-1α was mediated via S1P3, Gi/0, PI3K, PKCβI, ERK1/2, mTOR and translation factors p70S6K and eIF4E. Finally, it was shown that HIF-1α mediated S1P-induced migration. The ECM is constituted of a complex and coordinated assembly of many types of proteins. In order to be able to invade, cells need to break down the ECM, therefore several key players in this event were investigated in the second project. S1P increased the secretion and activity of MMP2 and MMP9 via S1P-receptor 1 and 3 and that these MMPs participated in the S1P-facilitated invasion of ML-1 cells. In this interplay, calpains and Rac1 were involved, both of which are crucial players in migration and invasion. The prognosis for some types of thyroid cancer is relatively good. However, there are forms of thyroid cancers, for which there are no treatments or the current available treatments are inefficient. Thus, new medical interventions are urgently needed. In the third project the significance of the S1P-receptor modulating drug FTY720, which is currently used for the treatment of multiple sclerosis (MS), was studied. The effect of FTY720 was tested on several thyroid cancer cell lines, and it inhibited the proliferation and invasion of all cancer cell lines tested. In ML-1 cells, FTY720 attenuated invasion by blocking signaling intermediates important for migration and invasion of the cells. Moreover, FTY720 inhibited the proliferation of ML-1 cells by increasing the expression of p21 and p27, hence, inducing cell arrest in G1 phase of the cell cycle. Thus, it can be suggested that FTY720 could be used in the treatment of thyroid cancer.

Prodrug strategies of antiviral nucleotides: Studies on enzymatically and thermally removable phosphate protecting groups

Antiviral nucleosides are compounds that are used against viruses, such as human immunodeficiency virus (HIV) and hepatitis C virus (HCV). To act as therapeutic agent, the antiviral nucleoside needs to be phosphorylated to nucleotide in the body in three consecutive phosphorylation steps by cellular or viral enzymes. The first phosphorylation to the nucleoside monophosphate is often inefficient and leads to poor antiviral activity. The antiviral efficacy can be improved by applying a prodrug strategy and delivering the antiviral nucleoside directly as its monophosphate. In prodrug strategies of antiviral nucleotides, the negative charges on the phosphate moiety are temporarily masked with protecting groups. Once inside the cell, the protecting groups are removed by enzymatic or chemical processes. Many prodrug strategies apply biodegradable protecting groups, the removal of which is triggered by esterase enzymes. Several studies have, however, demonstrated that the removal rate of the second and subsequent esterase labile protecting groups significantly slows down after the first protecting group is removed due to the negative charge on the phosphodiester intermediate, which disturbs the catalytic site of the enzyme. In this thesis, esterase labile protecting group strategies where the issue of retardation could be avoided were studied. Prodrug candidates of antiviral nucleotides were synthesized and kinetic studies on the chemical and enzymatic stability were carried out. In the synthesized compounds, the second protecting group is cleaved from the monophosphate some other mechanism than esterase triggered activation or the structure of prodrug requires only one protecting group. In addition, esterase labile protecting group which is additionally thermally removable was studied. This protecting group was cleaved from oligomeric phosphodiesters both enzymatically and thermally and seems most attractive of the studied phosphate protecting groups. However, the rate of the thermal removal still is too slow to allow efficient protection of longer oligonucleotides and needs optimization. Key words: antiviral, nucleotide, prodrug, protecting group, biodegradable

Novel cancer-related regulatory targets for the signalling sphingolipids sphingosine-1-phosphate and sphingosylphosphorylcholine

The signalling sphingolipid sphingosine-1-phosphate (S1P) is necessary for development of the immune system and vasculature and on a cellular level regulates migration, proliferation and survival. Due to these traits S1P has an important role in cancer biology. It is considered a primarily cancer-promoting factor and the enzyme which produces it, sphingosine kinase (SphK), is often over-expressed in tumours. S1P is naturally present in the blood, lymph, tissue fluids and cell cytoplasm and functions through its cell surface receptors (S1P1-5) and as an intracellular second messenger. Sphingosylphosphorylcholine (SPC) is closely related to S1P and has similar regulatory functions but has not been extensively studied. Both S1P and SPC are able to evoke either stimulatory or inhibitory effects on cancer cells depending on the context. The aim of this thesis work was to study novel regulatory targets of S1P and SPC, which mediate the effects of S1P/SPC signalling on cancer cell behaviour. The investigated targets are the transcription factor hypoxia-inducible factor 1 (HIF-1), the intermediate filament protein vimentin and components of the Hippo signalling pathway. HIF-1 has a central role in cancer biology, as it regulates a multitude of cancer-related genes and is potently activated by intratumoural hypoxia through stabilization of the regulatory subunit HIF-1α. Tumours typically harbour high HIF-1α levels and HIF-1, in turn, facilitates tumour angiogenesis and metastasis and regulates cancer cell metabolism. We found S1P to induce follicular thyroid cancer cell migration in normal oxygen conditions by increasing HIF-1α synthesis and stability and subsequently HIF-1 activity. Vimentin is a central regulator of cell motility and is also commonly over-expressed in cancers. Vimentin filaments form a cytoskeletal network in mesenchymal cells as well as epithelial cancer cells which have gone through epithelial-mesenchymal transition (EMT). Vimentin is heavily involved in cancer cell invasion and gives tumours metastatic potential. We saw both S1P and SPC induce phosphorylation of vimentin monomers and reorganization of the vimentin filament network in breast and anaplastic thyroid cancer cells. We also found vimentin to mediate the anti-migratory effect of S1P/SPC on these cells. The Hippo pathway is a novel signalling cascade which controls cancer-related processes such as cellular proliferation and survival in response to various extracellular signals. The core of the pathway consists of the transcriptional regulators YAP and TAZ, which activate predominantly cancer-promoting genes, and the tumour suppressive kinases Lats1 and Lats2 which inhibit YAP/TAZ. Increased YAP expression and activity has been reported for a wide variety of cancers. We found SPC to regulate Hippo signalling in breast cancer cells in a two-fold manner through effects on phosphorylation status, activity and/or expression of YAP and Lats2. In conclusion, this thesis reveals new details of the signalling function of S1P and SPC and regulation of the central oncogenic factors HIF-1 and vimentin as well as the novel cancer-related pathway Hippo.