Electrochemical properties of Cu4[PhN3C6H4N3(H)Ph]4(µ-O)2, a tetranuclear Copper(II) complex with 1-phenyltriazenido-2-phenyltriazene-benzene as ligand

Bis-(µ2-oxo)-tetrakis{[1-feniltriazene-1,3-diil)-2-(phenyltriazenil)benzene copper(II) is a tetranuclear complex which shows four Cu(II) ions coordinated by four 1,2-bis(phenyltriazene)benzene bridged ligands, with one diazoaminic deprotonated chain, and two O2- ligands. The complex reduces at E1/2 = -0.95 V vs Fc+/Fc, a two electrons process. Cyclic voltammetric and spectroelectrochemical studies showed a reversible process. When immobilized on carbon paste electrode, the complex electrocatalyses the reduction of O2 dissolved on aqueous solution at -0.3 V vs SCE potential. The obtained current shows linearity with O2 concentration.

Temporal variability of soil CO2 emission after conventional and reduced tillage described by an exponential decay in time model

To study Assessing the impact of tillage practices on soil carbon losses dependents it is necessary to describe the temporal variability of soil CO2 emission after tillage. It has been argued that large amounts of CO2 emitted after tillage may serve as an indicator for longer-term changes in soil carbon stocks. Here we present a two-step function model based on soil temperature and soil moisture including an exponential decay in time component that is efficient in fitting intermediate-term emission after disk plow followed by a leveling harrow (conventional), and chisel plow coupled with a roller for clod breaking (reduced) tillage. Emission after reduced tillage was described using a non-linear estimator with determination coefficient (R²) as high as 0.98. Results indicate that when emission after tillage is addressed it is important to consider an exponential decay in time in order to predict the impact of tillage in short-term emissions.

Pretreatment processes in gold recovery by thiosulphate leaching

This thesis describes several different pretreatment processes for gold concentrates and ores. The thesis is divided to theoretical part and experimental part. The theoretical part presents the operating principle of the main pretreatment methods and their suitability for thiosulphate leaching. In the theoretical part also the whole recovery process for gold from ore to elemental gold is presented. In the experimental part the study is focused on pretreatment of sulphidic refractory concentrates with mechanical activation and chemical oxidation under alkaline environment; and their effect on leachability in the thiosulphate leaching. In the experimental part a combined 2-step process, where chemical oxidation under ammoniacal environment is cascaded with thiosulphate leaching in the same conditions, is also tested. The main sulphuric mineral components in the studied refractory concentrate are pyrite (49.4 %) and arsenopyrite (27.7 %). The gold content in the concentrate is 11.3 ppm and silver content is 90 ppm. Without pretreatment the gold conversion in thiosulphate leaching was 30 %, which was analyzed at the time point of 9 hours. At that time the silver conversion was 17 %. By using mechanical activation the gold conversion reached was 59 % and silver conversion 26 %. With chemical oxidation under alkaline environment, where the used chemical was sodium hydroxide, the reached conversion of gold was 72 % and 31 % for silver. In the combined oxidation and leaching experiment the conversion of gold remained at 49 % and 18 % for silver.

Save Consumers Time and Money: Thou Shall Not Forget Digital Native Big Data Consumers

Poster at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Building Dynamic Data Centers for Fast Delivery of New Data and Data Updates

Poster at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

A Template for Cloud Technology Deployment in an Energy Trading Environment

Nykyaikaiset pilvipalvelut tarjoavat suurille yrityksille mahdollisuuden tehostaa laskennallista tietojenkäsittelyä. Pilvipalveluiden käyttöönotto tuo mukanaan kuitenkin esimerkiksi useita tietoturvakysymyksiä, joiden vuoksi käyttöönoton tulee olla tarkasti suunniteltua. Tämä tutkimus esittelee kirjallisuuskatsaukseen perustuvan, asteittaisen suunnitelman pilvipalveluiden käyttöönotolle energialiiketoimintaympäristössä. Kohdeyrityksen sisäiset haastattelut ja katsaus nykyisiin energiateollisuuden pilviratkaisuihin muodostavat kokonaiskuvan käyttöönoton haasteista ja mahdollisuuksista. Tutkimuksen päätavoitteena on esittää ratkaisut tyypillisiin pilvipalvelun käyttöönotossa esiintyviin ongelmiin käyttöönottomallin avulla. Tutkimuksessa rakennettu käyttöönottomalli testattiin esimerkkitapauksen avulla ja malli todettiin toimivaksi. Ulkoisten palveluiden herättämien tietoturvakysymysten takia käyttöönoton ensimmäiset osiot, kuten lopputuotteen määrittely ja huolellinen suunnittelu, ovat koko käyttöönottoprosessin ydin. Lisäksi pilvipalveluiden käyttöönotto vaatii nykyiseltä käyttöympäristöltä uusia teknisiä ja hallinnollisia taitoja. Tutkimuksen tulokset osoittavat pilvipalveluiden monipuolisen hyödyn erityisesti laskentatehon tarpeen vaihdellessa. Käyttöönottomallin rinnalle luotu kustannusvertailu tukee kirjallisuuskatsauksessa esille tuotuja hyötyjä ja tarjoaa kohdeyritykselle perusteen tutkimuksen eteenpäin viemiselle.

High expression of human carboxypeptidase M in Pichia pastoris: Purification and partial characterization

Carboxypeptidase M (CPM) is an extracellular glycosylphosphatidyl-inositol-anchored membrane glycoprotein, which removes the C-terminal basic residues, lysine and arginine, from peptides and proteins at neutral pH. CPM plays an important role in the control of peptide hormones and growth factor activity on the cell surface. The present study was carried out to clone and express human CPM in the yeast Pichia pastoris in order to evaluate the importance of this enzyme in physiological and pathological processes. The cDNA for the enzyme was amplified from total placental RNA by RT-PCR and cloned in the vector pPIC9, which uses the methanol oxidase promoter and drives the expression of high levels of heterologous proteins in P. pastoris. The cpm gene, after cloning and transfection, was integrated into the yeast genome, which produced the active protein. The recombinant protein was secreted into the medium and the enzymatic activity was measured using the fluorescent substrate dansyl-Ala-Arg. The enzyme was purified by a two-step protocol including gel filtration and ion-exchange chromatography, resulting in a 1753-fold purified active protein (16474 RFU mg protein-1 min-1). This purification protocol permitted us to obtain 410 mg of the purified protein per liter of fermentation medium. SDS-PAGE showed that recombinant CPM migrated as a single band with a molecular mass similar to that of native placental enzyme (62 kDa), suggesting that the expression of a glycosylated protein had occurred. These results demonstrate for the first time the establishment of a method using P. pastoris to express human CPM necessary to the development of specific antibodies and antagonists, and the analysis of the involvement of this peptidase in different physiological and pathological processes

Tasapaino taloudellisessa tulospalkkiojärjestelmässä: Kaksi näkökulmaa – Case Gigantti Oy

Tutkielmassa perehdytään tapaustutkimuksen muodossa Gigantti Oy:n Contact Center -liiketoimintayksikön tulospalkkiojärjestelmään tilikaudella 2014-2015. Palkitseminen on kaksisuuntainen prosessi, jonka takia hyvin toimivan tulospalkkiojärjestelmän tulee olla tasapainossa niin yritysjohdon, kuin henkilöstönkin näkökulmista tarkasteltuna. Laadullinen tutkimus pohjautuu työssä esitettyihin teorioihin, joiden pohjalta yksikössä suoritettiin henkilöstökysely kuvaamaan aihetta kokemuksen näkökulmasta, sekä haastattelu yksikön johtajan kanssa, kuvaten suunnittelun näkökulmaa.

Bio and chemocatalysis for stereo and regioselective one-pot reaction applications

The development of cost efficient, selective and sustainable chemical processes for production of chiral building blocks is of great importance in synthetic and industrial organic chemistry. One way to reach these objectives is to carry out several reactions steps in one vessel at one time. Furthermore, when this kind of one-pot multi step reactions are catalyzed by heterogeneous chemo- and bio-catalysts, which can be separated from the reaction products by filtration, practical access to chiral small molecules for further utilization can be obtained. The initial reactions studied in this thesis are the two step dynamic kinetic resolution of rac-2-hydroxy-1-indanone and the regioselective hydrogenation of 1,2-indanedione. These reactions are then combined in a new heterogeneously catalyzed one-pot reaction sequence enabling simple recovery of the catalysts by filtration, facilitating simple reaction product isolation. Conclusively, the readily available 1,2-indanedione is by the presented one-pot sequence, utilizing heterogeneous enzyme and transition metal based catalysts, transferred with high regio- and stereoselectivity to a useful chiral vicinal hydroxyl ketone structure. Additional and complementary investigation of homogeneous half-sandwich ruthenium complexes for catalyzing the epimerization of chiral secondary alcohols of five natural products containing additional non-functionalized stereocenters was conducted. In principle, this kind of epimerization reactions of single stereocenters could be utilized for converting inexpensive starting materials, containing other stereogenic centers, into diastereomeric mixtures from which more valuable compounds can be isolated by traditional isolation techniques.

Analysis and guidelines for implementation of EN 1090-2 Standard to assist execution class assignment of steel structures

Finnish design and consulting companies are delivering robust and cost-efficient steel structures solutions to a large number of manufacturing companies worldwide. Recently introduced EN 1090-2 standard obliges these companies to specify the execution class of steel structures for their customers. This however, requires clarifying, understanding and interpreting the sophisticated procedure of execution class assignment. The objective of this research is to provide a clear explanation and guidance through the process of execution class assignment for a given steel structure and to support the implementation of EN 1090-2 standard in Rejlers Oy, one of Finnish design and consulting companies. This objective is accomplished by creating a guideline for designers that elaborates on the four-step process of the execution class assignment for a steel structure or its part. Steps one to three define the consequence class (projected consequences of structure failure), the service category (hazards associated with the service use exploitation of steel structure) and the production category (manufacturing process peculiarities), based on the ductility class (capacity of structure to withstand deformations) and the behaviour factor (corresponds to structure seismic behaviour). The final step is the execution class assignment taking into account results of previous steps. Main research method is indepth literature review of European standards family for steel structures. Other research approach is a series of interviews of Rejlers Oy representatives and its clients, results of which have been used to evaluate the level of EN 1090-2 awareness. Rejlers Oy will use the developed novel coherent standard implementation guideline to improve its services and to obtain greater customer satisfaction.

Chemical changes in biomass during torrefaction

Torrefaction is moderate thermal treatment (~200-300 °C) of biomass in an inert atmosphere. The torrefied fuel offers advantages to traditional biomass, such as higher heating value, reduced hydrophilic nature, increased its resistance to biological decay, and improved grindability. These factors could, for instance, lead to better handling and storage of biomass and increased use of biomass in pulverized combustors. In this work, we look at several aspects of changes in the biomass during torrefaction. We investigate the fate of carboxylic groups during torrefaction and its dependency to equilibrium moisture content. The changes in the wood components including carbohydrates, lignin, extractable materials and ashforming matters are also studied. And at last, the effect of K on torrefaction is investigated and then modeled. In biomass, carboxylic sites are partially responsible for its hydrophilic characteristic. These sites are degraded to varying extents during torrefaction. In this work, methylene blue sorption and potentiometric titration were applied to measure the concentration of carboxylic groups in torrefied spruce wood. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic group contents. Thus, both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction. This provides new information to the chemical changes occurring during torrefaction. The effect of torrefaction temperature on the chemistry of birch wood was investigated. The samples were from a pilot plant at Energy research Center of the Netherlands (ECN). And in that way they were representative of industrially produced samples. Sugar analysis was applied to analyze the hemicellulose and cellulose content during torrefaction. The results show a significant degradation of hemicellulose already at 240 °C, while cellulose degradation becomes significant above 270 °C torrefaction. Several methods including Klason lignin method, solid state NMR and Py-GC-MS analyses were applied to measure the changes in lignin during torrefaction. The changes in the ratio of phenyl, guaiacyl and syringyl units show that lignin degrades already at 240 °C to a small extent. To investigate the changes in the extractives from acetone extraction during torrefaction, gravimetric method, HP-SEC and GC-FID followed by GC-MS analysis were performed. The content of acetone-extractable material increases already at 240 °C torrefaction through the degradation of carbohydrate and lignin. The molecular weight of the acetone-extractable material decreases with increasing the torrefaction temperature. The formation of some valuable materials like syringaresinol or vanillin is also observed which is important from biorefinery perspective. To investigate the change in the chemical association of ash-forming elements in birch wood during torrefaction, chemical fractionation was performed on the original and torrefied birch samples. These results give a first understanding of the changes in the association of ashforming elements during torrefaction. The most significant changes can be seen in the distribution of calcium, magnesium and manganese, with some change in water solubility seen in potassium. These changes may in part be due to the destruction of carboxylic groups. In addition to some changes in water and acid solubility of phosphorous, a clear decrease in the concentration of both chlorine and sulfur was observed. This would be a significant additional benefit for the combustion of torrefied biomass. Another objective of this work is studying the impact of organically bound K, Na, Ca and Mn on mass loss of biomass during torrefaction. These elements were of interest because they have been shown to be catalytically active in solid fuels during pyrolysis and/or gasification. The biomasses were first acid washed to remove the ash-forming matters and then organic sites were doped with K, Na, Ca or Mn. The results show that K and Na bound to organic sites can significantly increase the mass loss during torrefaction. It is also seen that Mn bound to organic sites increases the mass loss and Ca addition does not influence the mass loss rate on torrefaction. This increase in mass loss during torrefaction with alkali addition is unlike what has been found in the case of pyrolysis where alkali addition resulted in a reduced mass loss. These results are important for the future operation of torrefaction plants, which will likely be designed to handle various biomasses with significantly different contents of K. The results imply that shorter retention times are possible for high K-containing biomasses. The mass loss of spruce wood with different content of K was modeled using a two-step reaction model based on four kinetic rate constants. The results show that it is possible to model the mass loss of spruce wood doped with different levels of K using the same activation energies but different pre-exponential factors for the rate constants. Three of the pre-exponential factors increased linearly with increasing K content, while one of the preexponential factors decreased with increasing K content. Therefore, a new torrefaction model was formulated using the hemicellulose and cellulose content and K content. The new torrefaction model was validated against the mass loss during the torrefaction of aspen, miscanthus, straw and bark. There is good agreement between the model and the experimental data for the other biomasses, except bark. For bark, the mass loss of acetone extractable material is also needed to be taken into account. The new model can describe the kinetics of mass loss during torrefaction of different types of biomass. This is important for considering fuel flexibility in torrefaction plants.

Tuotesuunnittelu direktiiviperustaisesti

Onnistuneen tuotekehitysprojektin läpivieminen vaatii huolellisen alkusuunnittelun ennen varsinaista tuotteen kehityksen aloitusta. Projektin läpiviemiseksi esitetään usein malleja joissa tuotekehitysprojektissa edetään yksi vaihe kerrallaan ja siirrytään seuraavaan vasta, kun edellinen on valmis. Tämän perinteisen mallin rinnalle on tullut DFMA-suunnittelu, jossa murretaan kommunikaatiomuuri suunnittelun ja valmistuksen väliltä ja useita vaiheita tehdään samanaikaisesta. Näin saadaan valmistus- ja kokoonpanoystävällisiä tuotteita, joilla tuotteesta saatava kate voidaan maksimoida samalla kun tuotteen laatua saadaan parannettua. Teknisen kehityksen lisäksi on tuotekehitysprosessissa erottamattomana osana direktiivien asettamien vaatimusten huomioon ottaminen. Jo lähes kaikissa tuotteissa on oltava CE-merkintä. CE-merkinnällä tuotteen valmistaja ottaa täyden vastuun siitä, että tuote täyttää sitä koskevien direktiivien asettamat vaatimukset vaatimustenmukaisuudesta. Direktiivien asettamat vaatimukset on hyvä tiedostaa jo tuotteen suunnittelun alkuvaiheista lähtien, jotta nämä osataan ottaa heti huomioon ja jälkikäteen tehtäviltä muutoksilta vältytään. Teknisten ratkaisujen lisäksi tuotteen dokumentoinnilla on suuri rooli vaatimustenmukaisuuden täyttämisessä. Tuotteesta tulee koota tekninen tiedosto, joka sisältää kaikki tarpeelliset dokumentit, joilla tuotteen vaatimustenmukaisuus voidaan todeta. Teknisen tiedoston vaatimukset on hyvä tiedostaa jo suunnittelun alusta lähtien, jotta tarvittavat dokumentit osataan kerätä projektin aikana tekniseen tiedostoon. Tässä työssä kehitettiin peltier-jäähdytin, jollaiselle asiakkailta saadun palautteen perusteella oli markkinoilla tarve. Jäähdyttimen suunnittelussa käytettiin DFMA:n keinoja yksinkertaistamaan kokoonpanoa. Jäähdyttimelle tehtiin vaatimustenmukaisuustarkastelu, missä tarkasteltiin peltier-jäähdytintä koskevien direktiivien asettamia vaatimuksia ja mitä asioita näiden vaatimusten täyttämiseksi tuli huomioida.

Spectral Retinal Images Reconstruction

While red-green-blue (RGB) image of retina has quite limited information, retinal multispectral images provide both spatial and spectral information which could enhance the capability of exploring the eye-related problems in their early stages. In this thesis, two learning-based algorithms for reconstructing of spectral retinal images from the RGB images are developed by a two-step manner. First, related previous techniques are reviewed and studied. Then, the most suitable methods are enhanced and combined to have new algorithms for the reconstruction of spectral retinal images. The proposed approaches are based on radial basis function network to learn a mapping from tristimulus colour space to multi-spectral space. The resemblance level of reproduced spectral images and original images is estimated using spectral distance metrics spectral angle mapper, spectral correlation mapper, and spectral information divergence, which show a promising result from the suggested algorithms.

Chelated fluoroboron cations : synthesis and multinuclear nmr studies

The preparation of chelated difluoroboron cations (DD)BF2+, where DD is a saturated polydentate tertiary-amine or polydentate aromatic ligand, has been systematically studied by using multinuclear solution and solid state nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. Three new methods of synthesis of (DD)BF2+ cations are reported, and compared with the previous method of reacting a chelating donor with Et20.BF3. The methods most effective for aromatic donors such as 1,1O-phenanthroline are ineffective for saturated polydentate tertiary-amines like N,N,N' ,Nil ,Nil-pentamethyldiethylenetriamine. Polydentate tertiary-amine donors that form 5-membered rings upon bidentate chelation were found to chelate effectively when the BF2 source contained two leaving groups (a heavy halide and a Lewis base such as pyridine =pyr or isoxazole =ISOX), i.e., pyr.BF2X (X = CI or Br), ISOX.BF2X and (pyr)2BF2+. Those that would form 6membered rings upon chelation do not chelate by any of the four methods. Polydentate aromatic ligands chelate effectively when the BF2 source contained a weak Lewis base, e.g., ISOX.BF3, ISOX.BF2X and Et20.BF3. Bidentate chelation by polydentate tertiaryamine and aromatic donors leads to nmr parameters that are significantly different then their (D)2BF2+ relatives (D =monod~ntate t-amines or pyridines). The chelated haloboron cations (DD)BFCI+, and (DD)BFBr+ were generated from D.BFX2 adducts for all ligands that form BF2+ cations above. In addition, the (DD)BCI2+ and (DD)BBr2+ cations were formed from D.BX3 adducts by the chelating aromatic ligands, except for the aromatic ligand 1,8-bis(dimethylamino)naphthalene, which formed only the (DD)BF2+ cation, apparently due to its extreme steric hindrance. Chelation by a donor is a two-step reaction. For polydentate tertiary-amine ligands, the two rates appear to be very dependent on the two possible leaving groups on the central boron atom. The order of increasing ease of displacement for the donors was: pyr < Cl < Br < ISOX. The rate of chelation by polydentate aromatic ligands appears to be dependent on the displacement of the first ligand from the boron. The order of increasing ease of displacement for the donors was: pyr < CI < ISOX ~ Br < Et20.

The impact of hospital downsizing on registered nurses displaced from full-time employment

This research identified and explored the various responses often women Registered Nurses displaced from full-time elnployment as staff nurses in general hospitals in southern Ontario. These nurses were among the hundreds in Ontario who were displaced between October 1991 and October 1995 as a result of organizational downsizing and other health care reform initiatives. The purpose ofthis research was to document tIle responses of nurses to job displacement, and how that experience impacted on a nurse's professional identity and her understanding of the nature and utilization of nursing labour. This study incorporated techniques consistent with the principles of naturalistic inquiry and the narrative tradition. A purposive sample was drawn from the Health Sector Training and Adjustment Program database. Data collection and analysis was a three-step process wherein the data collection in each step was informed by the data analysis in the preceding step. The main technique used for qualitative data collection was semistructured, individual and group interviews. Emerging from the data was a rich and textured story ofhow job displacement disrupted the meaningful connections nurses had with their work. In making meaning of this change, displaced nurses journeyed along a three-step path toward labour adjustment. Structural analysis was the interpretive lens used to view the historical, sociopolitical and ideological forces which constrained the choices reasonably available to displaced nurses while Kelly's personal construct theory was the lens used to view the process of making choices and reconstruing their professional identity.