The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

Ultrastructural changes of Fusobacterium nucleatum as a defense mechanism against human neutrophil peptide-1 - A Transmission Electron Microscopy (TEM) study

Aims: The aim of this work was to assess the ultrastructural changes, cellular proliferation, and the biofilm formation ability of F. nucleatum as defense mechanisms against the effect of HNP-1. Materials and methods: The type strain of F. nucleatum (ssp. nucleatum ATCC 25586) and two clinical strains (ssp. polymorphum AHN 9910 and ssp. nucleatum AHN 9508) were cultured and incubated with four different test concentrations of recombinant HNP-1 (1, 5, 10 and 20 µg/ml) and one control group (0 µg/ml). Bacterial pellets from each concentration were processed for TEM imaging. Planktonic growth was assessed and colony forming units (CFU) were measured to determine the cellular proliferation. Scrambled HNP-1 was used for confirmation. Results: TEM analyses revealed a decrease in the outer membrane surface corrugations and roughness of the strain AHN 9508 with increasing HNP-1 concentrations. In higher concentrations of HNP-1, the strain AHN 9910 showed thicker outer membranes with a number of associated rough vesicles attached to the outer surface. For ATCC 25586, the treated bacterial cells contained higher numbers of intracellular granules with increasing the peptide concentration. Planktonic growth of the two clinical strains were significantly enhanced (P<0.001) with gradually increased concentrations of HNP-1. None of the planktonic growth results of the 3 strains incubated with the scrambled HNP-1 was statistically significant. HNP-1 decreased the biofilm formation of the two clinical strains, AHN 9910 and 9508, significantly (P<0.01 and P<0.001; respectively). Conclusions: The present in vitro study demonstrates that F. nucleatum has the ability to withstand the lethal effects of HNP-1 even at concentrations simulating the diseased periodontium in vivo. The increase in planktonic growth could act as defense mechanisms of F. nucleatum against HNP-1.

The Role of Structural Imperfections in Sr2FeMoO6 Thin Films

In this work, Sr2FeMoO6 (SFMO) thin films were studied with the main focus on their magnetic and magneto-transport properties. The fabrication process of pulsed laser deposited SFMO films was first optimized. Then the effects of strain, film thickness and substrate were thoroughly investigated. In addition to these external factors, the effect of intrinsic defects on the magnetic properties of SFMO were also clarified. Secondly, the magnetoresistivity mechanims of SFMO films were studied and a semiempirical model of the temperature dependence of resistivity was introduced. The films were grown on single crystal substrates using a ceramic target made with sol-gel method. The structural characterization of the films were carried out with X-ray diffraction, atomic force microscopy, transmission electron microscopy and high kinetic energy photoelectron spectroscopy. The magnetic properties were measured with SQUID magnetometer and the magneto-transport properties by magnetometer with a resistivity option. SFMO films with the best combination of structural and magnetic properties were grown in Ar atmosphere at 1050 °C . Their magnetic properties could not be improved by the ex situ post-annealing treatments aside from the treatments in ultra-high vacuum conditions. The optimal film thickness was found to be around 150 nm and only small improvement in the magnetic properties with decreasing strain was observed. Instead, the magnetic properties were observed to be highly dependent on the choice of the substrate due to the lattice mismatch induced defects, which are best avoided by using the SrTiO3 substrate. The large difference in the Curie temperature and the saturation magnetization between the SFMO thin film and polycrystalline bulk samples was connected to the antisite disorder and oxygen vacancies. Thus, the Curie temperature of SFMO thin films could be improved by increasing the amount of oxygen vacancies for example with ultra-high vacuum treatments or improving the B-site ordering by further optimization of the deposition parameters. The magneto-transport properties of SFMO thin films do not follow any conventional models, but the temperature dependence of resistivity was succesfully described with a model of two spin channel system. Also, evidences that the resistivity-temperature behaviour of SFMO thin films is dominated by the structural defects, which reduce the band gap in the majority spin band were found. Moreover, the magnetic field response of the resistivity in SFMO thin films were found to be superposition of different mechanisms that seems to be related to the structural changes in the film.

Yritysvalmennuksen onnistumiset ja kehittämiskohteet Case: Start-up & Spin-off Factory -projekti

Tässä työssä tarkastellaan Start-up & Spin-off Factory -projektissa, pääsääntöisesti Kymenlaaksossa toimiville, yrittäjille suunnattua ja toteutettua yritysvalmennusohjelmaa. Työssä selvitetään ja käsitellään Start-up & Spin-off -projektin yritysvalmennuksen onnistumisia ja kehittämiskohteita sähköisen kyselyn sekä teemahaastatteluiden pohjalta. Start-up & Spin-off Factory -projektissa tuettiin innovatiivisten yritysten (21 yritystä) kasvua kiihdytysohjelmalla, jossa kokeneet sarjayrittäjät valmensivat uutta yritystä perustavia tai jo yritystoiminnan aloittaneita yrittäjiä, joiden tuotteille/palveluille haluttiin saada kasvua. Projektin tavoitteena oli edistää erityisesti kiihdytettävien yritysten nopeaa kansainvälistymistä auttamalla yrittäjiä pilottien, asiakkaiden, partnerien ja rahoituksen hankinnassa. Valmennettavat kokivat saaneensa lisäarvoa valmennuksesta omaksumalla uusia näkökulmia. He kokivat koulutuksen tuoneen yrityksen toimintaan lisää nöyrää asennetta ja lujaa uskoa tulevaisuuteen. Vertaistuen osuutta sekä verkostojen lisääntymisen mukana tullutta uusien kontaktien määrää pidettiin myönteisenä asiana. Vastausten perusteella valmennus selkeytti valmennettavien ymmärrystä liiketoiminnan kehittämisestä. Hissipuheen teko ja harjoittelu koettiin tärkeäksi ja jännittäväksi. Valmennus vahvisti luottamusta omaan tuotteeseen ja palveluun. Valmennuksen painottuminen ICT-alan firmoihin merkitsi valmennuksessa sitä, että teoriat ja esimerkit tulivat useasti tältä alalta. Toimialojen eroavaisuus tulisi huomioida valmennuksessa opetussisältöjen ja esimerkkien osalta. Kyselyn ja haastatteluiden mukaan valmentajien asiantuntemukseen oltiin tyytyväisiä. Lisäksi onnistuneena osa-alueena koettiin valmennuksen käytännön järjestelyjä. Kehitettävää puolestaan oli opetusmateriaalien, opetusmenetelmien ja koulutuksen keston suhteen. Kysyttäessä valmennuksen hyvistä ja huonoista puolista olivat vastaajat sitä mieltä, että valmennuksessa oli hyvä ilmapiiri ja valmennus oli käytännönläheistä. Pienryhmävalmennusta pidettiin hyvänä asiana, samoin kuin henkilökohtaistamista.

Nanoclustering augmentation : a novel mechanism of Ras activation in cancer

Proteins of the Ras family are central regulators of crucial cellular processes, such as proliferation, differentiation and apoptosis. Their importance is emphasized in cancer, in which the isoforms H-ras, N-ras and K-ras are misregulated by mutations in approximately 20 – 30 % of cases. Thus, they represent major cancer oncogenes and one of the most important targets for cancer drug development. Ras proteins are small GTPases, which cycle between the GTP-bound active and GDP-bound inactive state. Despite the tremendous research conducted in the last three decades, many fundamental properties of Ras proteins remain poorly understood. For instance, although new concepts have recently emerged, the understanding of Ras behavior in its native environment, the membrane, is still largely missing. On the membrane Ras organizes into nanoscale clusters, also called nanoclusters. They differ between isoforms, but also between activation states of Ras. It is considered that nanoclusters represent the basic Ras signaling units. Recently, it was demonstrated that on the membrane Ras adopts distinct conformations, the so-called orientations, which are dependent on the Ras activations state. The membrane-orientation of H-ras is stabilized by the helix α4 and the C-terminal hypervariable region (hvr). The novel switch III region was proposed to be involved in mediating the change between different H-ras orientations. When the regions involved in this mechanism are mutated, H-ras activity is changed by an unknown mechanism. This thesis has explained the connection between the change of Ras orientation on the membrane and Ras activity. We demonstrated that H-ras orientation mutants exhibit altered diffusion properties on the membrane, which reflect the changes in their nanoclustering. The altered nanoclustering consequently rules the activity of the mutants. Moreover, we demonstrated that specific cancer-related mutations, affecting the switch III region of different Ras isoforms, exhibit increased nanoclustering, which consequently leads to stronger Ras signaling and tumorigenicity. Thus, we have discovered nanoclustering increase as a novel mechanism of Ras activity modulation in cancer. The molecular architecture of complexes formed on the membrane upon Ras activation is another poorly understood property of Ras. The following work has provided novel details on the regulation of Ras nanoclustering by a known H-ras-GTP nanoclustering stabilizer galectin-1 (Gal-1). Our study demonstrated that Gal-1 is not able to bind Ras directly, as it was previously proposed. Instead, its effect on H-ras-GTP nanoclustering is indirect, through binding of the effector proteins. Collectively, our findings represent valuable novel insights in the behavior of Ras, which will help the future research to eventually develop new strategies to successfully target Ras in cancer.

Coopetition as a lead generating mechanism: design, modelling and simulation

The aim of this research is to develop a tool that could allow to organize coopetitional relationships between organizations on the basis of two-sided Internet platform. The main result of current master thesis is a detailed description of the concept of the lead generating internet platform-based coopetition. With the tools of agent-based modelling and simulation, there were obtained results that could be used as a base for suggestion that the developed concept is able to cause a positive effect on some particular industries (e.g. web-design studios market) and potentially can bring some benefits and extra profitability for most companies that operate on this particular industry. Also on the basis of the results it can be assumed that the developed instrument is also able to increase the degree of transparency of the market to which it is applied.

Suomalaisten yliopistojen life science-alan spin-off-yritysten rahoitustilanne, -lähteet ja –riskit

Life science-ala on rahoituksellisesti erittäin haastava, koska tuotekehitysputket ovat 10-15 vuoden pituisia ja voivat vaatia suuria etupainotteisia investointeja. Monet life science-alan yritykset ovat niin Suomessa kuin kansainvälisestikin syntyneet suoraan yliopistosta niin sanottuina spin-off-yrityksinä. Yrityksen perustaminen tutkimustiedon pohjalle on yksi akateemisen yrittäjyyden muodoista. Tässä tutkimuksessa tutkitaan akateemista yrittäjyyttä life science-alalla Suomessa. Suomessa life science-alan osaaminen on kansainvälistä huippua ja alalle on syntynyt useita spin-off-yrityksiä viime vuosina. Aiemmat tutkimukset ovat keskittyneet erityisesti agentti-päämiesongelmiin akateemisessa yrittäjyydessä ja life science alaa puolestaan on käsitelty usein pelkästään yhtenä alana. Tutkimuksessa pyritään analysoimaan life science-alan eri painopiste-alueita tarkemmin rahoitusstrategisesta näkökulmasta, koska ala ei ole homogeeninen. Akateemisen yrittäjyyden agenttiongelmaa pyritään tarkoittamaan Suomen yliopistomaailmassa life science-alalta käsin. Tutkimus toteutetaan kvalitatiivisena haastattelututkimuksena ja sitä tukevana tilinpäätöstietojen analysointina. Tutkimuksen tulokset vahvistavat agentti-päämiesongelmien olemassaolon suomalaisessa yliopistomaailmassa. Ongelmien osapuolina ovat niin akateemikot, yliopiston innovaatiopalvelut kuin TEKES:kin. Yrittäjät kaipaavat kokonaisvaltaisempaa apua, koska kokevat alalla liiketoimintaosaamisen puuttuvan monin paikoin. Alan vaatimien runsaiden tuotekehityspanostusten vuoksi alan yritykset ovat pitkään raskaasti tappiollisia. Yritysten valitsemat rahoitusratkaisut vaihtelevat suuresti. Kaikki tutkitut yritykset pyrkivät kasvamaan nykyisten ydintuotteidensa mukana ja ovat jo jossain määrin hankkineet rahoitusta kasvustrategiaansa varten. Alan pääomaintensiivisyydestä johtuen ovat monet yritykset kuitenkin suunnittelemassa tai jo päätyneet tekemään yhteistyötä integroituen alalla joko vertikaalisesti tai horisontaalisesti. Tutkimuksen tulokset vahvistavat aiemman käsityksen, jonka mukaan life science-alan yrityksiä on vaikea arvioida ulkopuolelta pelkästään tilinpäätöstietojen pohjalta, koska alkuvaiheessa rahoituskierrokset ja tappiolliset vuoden seuraavat toisiaan ja toisaalta yrityksen arvo sitoutuu pitkiin tuotekehitysputkiin, jotka eivät välttämättä näy tilinpäätöksessä. Tulokset tuovat esille merkittäviä yritysten kokemia ongelmia rahoituksen saannissa life science-alalla Suomessa sekä akateemisen yrittäjyyden epäkohtia yritystoiminnan näkökulmasta. Näiden tekijöiden huomioonottaminen ja laajempi kansainvälinen vertailu voivat auttaa suomalaisia yrityksiä tällä vahvalla osaamisalalla eteenpäin.