System-level characterization of Th2 cell development and immune cell responses to ZnO and TiO2 nanoparticles

Asthma and allergy are common diseases and their prevalence is increasing. One of the hypotheses that explains this trend is exposure to inhalable chemicals such as traffi c-related air pollution. Epidemiological research supports this theory, as a correlation between environmental chemicals and allergic respiratory diseases has been found. In addition to ambient airborne particles, one may be exposed to engineered nanosized materials that are actively produced due to their favorable physico-chemical properties compared to their bulk size counterparts. On the cellular level, improper activity of T helper (Th) cells has been connected to allergic reactions. Th cells can differentiate into functionally different effector subsets, which are identifi ed according to their characteristic cytokine profi les resulting in specifi c ability to communicate with other cells. Th2 cells activate humoral immunity and stimulate eradication of extracellular pathogens. However, persistent predominance of Th2 cells is involved in a development of number of allergic diseases. The cytokine environment at the time of antigen recognition is the major factor determining the polarization of a naïve Th cell. Th2 cell differentiation is initiated by IL4, which signals via transcription factor STAT6. Although the importance of this pathway has been evaluated in the mouse studies, the signaling components involved have been largely unknown. The aim of this thesis was to identify molecules, which are under the control of IL4 and STAT6 in Th cells. This was done by using system-level analysis of STAT6 target genes at genome, mRNA and protein level resulting in identifi cation of various genes previously not connected to Th2 cell phenotype acquisition. In the study, STAT6-mediated primary and secondary target genes were dissection from each other and a detailed transcriptional kinetics of Th2 cell polarization of naïve human CD4+ T cells was collected. Integration of these data revealed the hierarchy of molecular events that mediates the differentiation towards Th2 cell phenotype. In addition, the results highlighted the importance of exploiting proteomics tools to complement the studies on STAT6 target genes identifi ed through transcriptional profi ling. In the last subproject, the effects of the exposure with ZnO and TiO2 nanoparticles was analyzed in Jurkat T cell line and in primary human monocyte-derived macrophages and dendritic cells to evaluate their toxicity and potential to cause infl ammation. Identifi cation of ZnO-derived gene expression showed that the same nanoparticles may elicit markedly distinctive responses in different cell types, thus underscoring the need for unbiased profi ling of target genes and pathways affected. The results gave additional proof that the cellular response to nanosized ZnO is due to leached Zn2+ ions. The approach used in ZnO and TiO2 nanoparticle study demonstrated the value of assessing nanoparticle responses through a toxicogenomics approach. The increased knowledge of Th2 cell signaling will hopefully reveal new therapeutic nodes and eventually improve our possibilities to prevent and tackle allergic infl ammatory diseases.

Professional sports and gambling regulation in Finland - Examining the institutional factors of gambling affecting professional sport clubs in Finland

This study examines how to institutional environment of gambling is currently in motion both in Europe and Finland. Furthermore, it examines the criticism by Finnish professional sport clubs directed towards the national gambling monopolies, especially Veikkaus Oy. This criticism addresses the acclaimed issue of low or non-existing sponsorship funds coming to the clubs despite the clubs’ duties to promote Veikkaus Oy in their stadiums etc. In essence the main research objective was to examine the interaction and institutional environments of both Finnish professional sport clubs and gambling regulation. This was done through three sub-objectives: 1) to analyze professional sport as business and its institutional environment 2) to analyze the institutions of gambling in their current state and their potential future 3) to evaluate the potential impact of an institutional change in gambling legislation to the professional sport clubs The findings from Finland were then compared to those of Denmark where an institutional change had occurred in gambling regulation. Empirical data was collected through multiple interviews. Interviewees represented sport clubs (7), sport association (1), sport league (1), Finnish monopoly representatives (2), commercial gambling providers (1), Danish monopoly system representatives (1), Danish sport club (1). In addition a vast amount of secondary data (e.g. Green and white books by EU, court decisions, a variety of studies etc.). Theoretically this study combines the aspects of institutional theory with the theory of professional sports as business. This proved to be a rather new approach and no published literature was found to have done specifically this. The findings of this study are twofold, on the European level it is clear that the momentum if towards a more liberated gambling market while Finland is at the moment trying to go the opposite direction and uphold its monopoly. From the sport club’s level the findings suggest that currently sport clubs do not directly benefit from the funds originated from Veikkaus Oy as these funds are more or less used on the association/league levels. However, the clubs themselves are also lacking in self-criticism as they are lacking in clear sponsorship packages/programs which Veikkaus Oy might be interested in participating. If liberation of the gambling market would occur it is highly possible that that the largest clubs in football and ice-hockey would be the main beneficiaries while smaller clubs and sports could possibly be worse off than currently. These interpretations were well supported by the findings from Denmark.

Acceleration of Solar Energetic Particles in coronal shocks through self-generated turbulence

The acceleration of solar energetic particles (SEPs) by flares and coronal mass ejections (CMEs) has been a major topic of research for the solar-terrestrial physics and geophysics communities for decades. This thesis discusses theories describing first-order Fermi acceleration of SEPs through repeated crossings at a CME-driven shock. We propose that particle trapping occurs through self-generated Alfvén waves, leading to a turbulent trapping region in front of the shock. Decelerating coronal shocks are shown to be capable of efficient SEP acceleration, provided seed particle injection is sufficient. Quasi-parallel shocks are found to inject thermal particles with good efficiency. The roles of minimum injection velocities, cross-field diffusion, downstream scattering efficiency and cross-shock potential are investigated in detail, with downstream isotropisation timescales having a major effect on injection efficiency. Accelerated spectra of heavier elements up to iron are found to exhibit significantly harder spectra than protons. Accelerated spectra cut-off energies are found to scale proportional to (Q/A)^1.5, which is explained through analysis of the spectral shape of amplified Alfvénic turbulence. Acceleration times to different threshold energies are found to be non-linear, indicating that self-consistent time-dependent simulations are required in order to expose the full extent of acceleration dynamics. The well-established quasilinear theory (QLT) of particle scattering is investigated by comparing QLT scattering coefficients with those found via full-orbit simulations. QLT is found to overemphasise resonance conditions. This finding supports the simplifications implemented in the presented coronal shock acceleration (CSA) simulation software. The CSA software package is used to simulate a range of acceleration scenarios. The results are found to be in agreement with well-established particle acceleration theory. At the same time, new spatial and temporal dynamics of particle population trapping and wave evolution are revealed.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Modeling of Liquid-Solid Flow in Industrial Scale

In the present work, liquid-solid flow in industrial scale is modeled using the commercial software of Computational Fluid Dynamics (CFD) ANSYS Fluent 14.5. In literature, there are few studies on liquid-solid flow in industrial scale, but any information about the particular case with modified geometry cannot be found. The aim of this thesis is to describe the strengths and weaknesses of the multiphase models, when a large-scale application is studied within liquid-solid flow, including the boundary-layer characteristics. The results indicate that the selection of the most appropriate multiphase model depends on the flow regime. Thus, careful estimations of the flow regime are recommended to be done before modeling. The computational tool is developed for this purpose during this thesis. The homogeneous multiphase model is valid only for homogeneous suspension, the discrete phase model (DPM) is recommended for homogeneous and heterogeneous suspension where pipe Froude number is greater than 1.0, while the mixture and Eulerian models are able to predict also flow regimes, where pipe Froude number is smaller than 1.0 and particles tend to settle. With increasing material density ratio and decreasing pipe Froude number, the Eulerian model gives the most accurate results, because it does not include simplifications in Navier-Stokes equations like the other models. In addition, the results indicate that the potential location of erosion in the pipe depends on material density ratio. Possible sedimentation of particles can cause erosion and increase pressure drop as well. In the pipe bend, especially secondary flows, perpendicular to the main flow, affect the location of erosion.

Studies in selectivity of lipases in preparation of cyanohydrins, sugar conjugates and secondary alcohols

Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.

Entrepreneurship Education in Basic and Upper Secondary Education – Measurement and Empirical Evidence

The starting point of this study is to direct more attention to the teacher and those entrepreneurship education practices taking place in formal school to find out solutions for more effective promotion of entrepreneurship education. For this objective, the strategy-level aims of entrepreneurship education need to be operationalised into measurable and understandable teacher-level practices. Furthermore, to enable the effective development of entrepreneurship education in basic and upper secondary level education, more knowledge is needed of the state of affairs of entrepreneurship education in teaching. The purpose of the study is to increase the level of understanding of teachers’ entrepreneurship education practices, and through this to develop entrepreneurship education. This study builds on the literature on entrepreneurship education and especially those elements referring to the aims, resources, benefits, methods, and practises of entrepreneurship education. The study comprises five articles highlighting teachers’ role in entrepreneurship education. In the first article the concept of entrepreneurship and the teachers role in reflection upon his/hers approaches to entrepreneurship education are considered. The second article provides a detailed analysis of the process of developing a measurement tool to depict the teachers’ activities in entrepreneurship education. The next three articles highlight the teachers’ role in directing the entrepreneurship education in basic and upper secondary level education. Furthermore, they analyse the relationship between the entrepreneurship education practises and the teachers’ background characteristics. The results of the study suggest a wide range of conclusions and implications. First, in spite of many outspoken aims connected to entrepreneurship education, teachers have not set any aims for themselves. Additionally, aims and results seem to mix. However, it is possible to develop teachers’ target orientation by supporting their reflection skills, and through measurement and evaluation increase their understanding of their own practices. Second, applying a participatory action process it is possible to operationalise teachers’entrepreneurship education practices. It is central to include the practitioners’ perspective in the development of measures to make sure that the concepts and aims of entrepreneurship education are understood. Third, teachers’ demographic or tenure-related background characteristics do not affect their entrepreneurship education practices, but their training related to entrepreneurship education, participation in different school-level or regional planning, and their own capabilities support entrepreneurship education. Fourth, a large number of methods are applied to entrepreneurship education, and the most often used methods were different kinds of discussions, which seem to be an easy, low-threshold way for teachers to include entrepreneurship education regularly in their teaching. Field trips to business enterprises or inviting entrepreneurs to present their work in schools are used fairly seldom. Interestingly, visits outside the school are more common than visitors invited to the school. In line, most of the entrepreneurship education practices take place in a classroom. Therefore it seems to be useful to create and encourage teachers towards more in-depth cooperation with companies (e.g. via joint projects) and to network systematically. Finally, there are plenty of resources available for entrepreneurship education, such as ready-made materials, external stakeholders, support organisations, and learning games, but teachers have utilized them only marginally.

Simulation of the Interaction Mean Free Path between Neutrons and TRISO Particles

The interaction mean free path between neutrons and TRISO particles is simulated using scripts written in MATLAB to solve the increasing error present with an increase in the packing factor in the reactor physics code Serpent. Their movement is tracked both in an unbounded and in a bounded space. Their track is calculated, depending on the program, linearly directly using the position vectors of the neutrons and the surface equations of all the fuel particles; by dividing the space in multiple subspaces, each of which contain a fraction of the total number of particles, and choosing the particles from those subspaces through which the neutron passes through; or by choosing the particles that lie within an infinite cylinder formed on the movement axis of the neutron. The estimate from the current analytical model, based on an exponential distribution, for the mean free path, utilized by Serpent, is used as a reference result. The results from the implicit model in Serpent imply a too long mean free path with high packing factors. The received results support this observation by producing, with a packing factor of 17 %, approximately 2.46 % shorter mean free path compared to the reference model. This is supported by the packing factor experienced by the neutron, the simulation of which resulted in a 17.29 % packing factor. It was also observed that the neutrons leaving from the surfaces of the fuel particles, in contrast to those starting inside the moderator, do not follow the exponential distribution. The current model, as it is, is thus not valid in the determination of the free path lengths of the neutrons.

Pulsed electric field assisted sol-gel preparation of TiO2 particles and their photocatalytic properties

The objective of this thesis was to study the effect of pulsed electric field on the preparation of TiO2 nanoparticles via sol-gel method. The literature part deals with properties of different TiO2 crystal forms, principles of photocatalysis, sol-gel method and pulsed electric field processing. It was expected that the pulsed electric field would have an influence on crystallite size, specific surface area, polymorphism and photocatalytic activity of produced particles. TiO2 samples were prepared by using different frequencies and treatment times of pulsed electric field. The properties of produced TiO2 particles were examined X-ray diffraction (XRD), Raman spectroscopy and BET surface area analysis. The photocatalytic activities of produced TiO2 particles were determined by using them as photocatalysts for the degradation of formic acid under UVA-light. The photocatalytic activities of samples produced with sol-gel method were also compared with the commercial TiO2 powder Aeroxide® (Evonic Degussa GmbH). Pulsed electric field did not have an effect on the morphology of particles. Results from XRD and Raman analysis showed that all produced TiO2 samples were pure anatase. However, pulsed electric field did have an effect on crystallite size, specific surface area and photocatalytic activity of TiO2 particles. Generally, the crystallite sizes were smaller, specific surface areas larger and initial formic acid degradation rates higher for samples that were produced by applying the pulsed electric field. The higher photocatalytic activities were attributed to larger surface areas and smaller crystallite sizes. Though, with all of the TiO2 samples produced by the sol-gel method the initial formic acid degradation rates were significantly slower than with the commercial TiO2 powder.

Track of HSMS Sophia tracing the extent of navigable water along the main northern ice between Spitzbergen and Greenland September 1868 : also showing the nature of the ice and temperature and depth of the sea

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Atomic Force Microscopy Investigation of NI Particles Deposited on Porous Silicon

In this thesis properties and influence of modification techniques of porous silicon were studied by Atomic Force Microscope (AFM). This device permits to visualize the surface topography and to study properties of the samples on atomic scale, which was necessary for recent investigation. Samples of porous silicon were obtained by electrochemical etching. Nickel particles were deposited by two methods: electrochemical deposition and extracting from NiCl2 ethanol solution. Sample growth was conducted in Saint-Petersburg State Electrotechnical University, LETI. Kelvin probe force microscopy (KPFM) and Magnetic force microscopy (MFM) were utilized for detailed information about surface properties of the samples. Measurements showed the difference in morphology correlating with initial growth conditions. Submicron size particles were clearly visible on surfaces of the treated samples. Although their nature was not clarified due to limitations of AFM technique. It is expected that surfaces were covered by nanometer scale Ni particles, which can be verified by implication of RAMAN device.

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.