Oxygen Photoreduction in Cyanobacteria

Cyanobacteria are well-known for their role in the global production of O2 via photosynthetic water oxidation. However, with the use of light energy, cyanobacteria can also reduce O2. In my thesis work, I have investigated the impact of O2 photoreduction on protection of the photosynthetic apparatus as well as the N2-fixing machinery. Photosynthetic light reactions produce intermediate radicals and reduced electron carriers, which can easily react with O2 to generate various reactive oxygen species. To avoid prolonged reduction of photosynthetic components, cyanobacteria use “electron valves” that dissipate excess electrons from the photosynthetic electron transfer chain in a harmless way. In Synechocystis sp. PCC 6803, flavodiiron proteins Flv1 and Flv3 comprise a powerful electron sink redirecting electrons from the acceptor side of Photosystem I to O2 and reducing it directly to water. In this work, I demonstrate that upon Ci-depletion Flv1/3 can dissipate up to 60% of the electrons delivered from Photosystem II. O2 photoreduction by Flv1/3 was shown to be vital for cyanobacteria in natural aquatic environments and deletion of Flv1/3 was lethal for both Synechocystis sp. PCC 6803 and Anabaena sp. PCC 7120 under fluctuating light conditions. The lethal phenotype observed in the absence of Flv1/3 results from oxidative damage to Photosystem I, which appeared to be a primary target of reactive oxygen species produced upon sudden increases in light intensity. Importantly, cyanobacteria also possess other O2 photoreduction pathways which can protect the photosynthetic apparatus. This study demonstrates that respiratory terminal oxidases are also capable of initiating O2 photoreduction in mutant cells lacking the Flv1/3 proteins and grown under fluctuating light. Photoreduction of O2 by Rubisco was also shown in Ci-depleted cells of the mutants lacking Flv1/3, and thus provided the first evidence for active photorespiratory gas-exchange in cyanobacteria. Nevertheless, and despite the existence of other O2 photoreduction pathways, the Flv1/3 route appears to be the most robust and rapid system of photoprotection. Several groups of cyanobacteria are capable of N2 fixation. Filamentous heterocystous N2- fixing species, such as Anabaena sp. PCC 7120, are able to differentiate specialised cells called heterocysts for this purpose. In contrast to vegetative cells which perform oxygenic photosynthesis, heterocysts maintain a microoxic environment for the proper function of the nitrogenase enzyme, which is extremely sensitive to O2. The genome of Anabaena sp. PCC 7120 harbors two copies of genes encoding Flv1 and Flv3 proteins, designated as “A” and “B” forms. In this thesis work, I demonstrate that Flv1A and Flv3A are expressed only in the vegetative cells of filaments, whilst Flv1B and Flv3B are localized exclusively in heterocysts. I further revealed that the Flv3B protein is most responsible for the photoreduction of O2 in heterocysts, and that this reaction plays an important role in protection of the N2-fixing machinery and thus, the provision of filaments with fixed nitrogen. The function of the Flv1B protein remains to be elucidated; however the involvement of this protein in electron transfer reactions is feasible. Evidence provided in this thesis indicates the presence of a great diversity of O2 photoreduction reactions in cyanobacterial cells. These reactions appear to be crucial for the photoprotection of both photosynthesis and N2 fixation processes in an oxygenic environment.

A performance analysis of conventional and fundamental exchange traded funds: ETFs and their risk-return characteristics in relation to building institutional investor’s passive portfolio

An exchange traded fund (ETF) is a financial instrument that tracks some predetermined index. Since their initial establishment in 1993, ETFs have grown in importance in the field of passive investing. The main reason for the growth of the ETF industry is that ETFs combine benefits of stock investing and mutual fund investing. Although ETFs resemble mutual funds in many ways, also many differences occur. In addition, ETFs not only differ from mutual funds but also differ among each other. ETFs can be divided into two categories, i.e. market capitalisation ETFs and fundamental (or strategic) ETFs, and further into subcategories depending on their fundament basis. ETFs are a useful tool for diversification especially for a long-term investor. Although the economic importance of ETFs has risen drastically during the past 25 years, the differences and risk-return characteristics of fundamental ETFs have yet been rather unstudied area. In effect, no previous research on market capitalisation and fundamental ETFs was found during the research process. For its part, this thesis seeks to fill this research gap. The studied data consist of 50 market capitalisation ETFs and 50 fundamental ETFs. The fundaments, on which the indices that the fundamental ETFs track, were not limited nor segregated into subsections. The two types of ETFs were studied at an aggregate level as two different research groups. The dataset ranges from June 2006 to December 2014 with 103 monthly observations. The data was gathered using Bloomberg Terminal. The analysis was conducted as an econometric performance analysis. In addition to other econometric measures, the methods that were used in the performance analysis included modified Value-at-Risk, modified Sharpe ratio and Treynor ratio. The results supported the hypothesis that passive market capitalisation ETFs outperform active fundamental ETFs in terms of risk-adjusted returns, though the difference is rather small. Nevertheless, when taking into account the higher overall trading costs of the fundamental ETFs, the underperformance gap widens. According to the research results, market capitalisation ETFs are a recommendable diversification instrument for a long-term investor. In addition to better risk-adjusted returns, passive ETFs are more transparent and the bases of their underlying indices are simpler than those of fundamental ETFs. ETFs are still a young financial innovation and hence data is scarcely available. On future research, it would be valuable to research the differences in risk-adjusted returns also between the subsections of fundamental ETFs.

Development of Rouble Exchange Rate in Russia

This 45th volume deals with the development of the Russian rouble, which suffered a severe depreciation crisis in 1998. In the aftermath of this event, a strong investment boom started in Russia. The new devalued rouble exchange rate gave price competitiveness to local industry. In addition to that, increasing export prices of Russian oil and natural gas deliveries have contributed to economic growth lately. Amid this boom period, inflationary pressure has remained high. Price increases have been higher than in the EU, Russia’s main trading partner. However, rouble/euro exchange rate has remained nominally rather stable in the current decade. This means, that rouble appreciates against euro in real terms, which is weakening Russia’s international competitiveness.

Deregulation of Railroads and Future Development Scenarios in Europe - Literature Analysis of Privatization Process Taken Place in US, UK and Sweden

Euroopan unionissa päätettiin jo yli vuosikymmen sitten, että rautatieliiketoiminta vapautetaan kilpailulle. Iso-Britanniasta olimäärä tulla esimerkkivaltio tämän prosessin käyttöönotossa. Pääideana oli säännöstelyn keventäminen, jolloin omistuspohja toimialalla laajenee ja rautateiden infrastruktuuri sekä toiminta parantuvat. Infrastruktuuri on määrä olla yhden organisaation hallinnassa ja raiteiden käyttöoikeus on kaikilla lupaehdot täyttävillä operaattoreilla, jotka kilpailevat keskenään matkustajista ja tavararahdeista. Kuitenkin Yhdysvalloissa ja eräissä Latinalaisen Amerikan maissa kilpailu on vapautettu siten, että rautatieyritys omistaa raideinfrastruktuurin, junat, tavarankuljetus- sekä matkustajavaunut. Iso-Britannian yksityistämistä pidettiin aluksi isonaepäonnistumisena: nopealla aikataululla sovellettiin jäykkiä transaktioperusteisia ulkoistamisstrategioita infrastruktuurin kunnossapitoon, jotka lopulta johtivat junien jatkuviin myöhästymisiin ja muutamaan tuhoisaan onnettomuuteen. Liiketoiminnallisessa mielessäkään ei oikein onnistuttu: infrastruktuurista vastaava yritys jouduttiin listaamaan pois Lontoon pörssistä, ja hallituksen oli pakko luoda tukipaketti pahasti velkaantuneen, vain marginaalisien investointien kohteena olleen yrityksen toimintaa varten (vaikka kapasiteettitarvetta oli markkinoilla). Myös rautatieoperaattorit olivat taloudellisessa ahdingossa ja vain määrätietoisten hallituksen laatimien pelastuspakettien avulla ala nousi syvimmästä kriisistään. Tästä huolimatta näiden negatiivisten sivuvaikutusten ohella koko ala pystyi kasvattamaan kysyntää, niin matkustaja- kuin rahtiliikenteenkin osalta. Vähenevän kysynnän trendi, joka alkoi 1970-luvulla, otti käännöksen parempaan. Toinen eurooppalaismaa, jolla on pitkät kokemukset yksityistämisestä, on Ruotsi. Tämä maatapaus on melko konservatiivinen verrattuna tilanteeseen edellisessä; vain rajattu määrä reittejä on avattu kilpailulle ja sopimukset tehdään kerralla pitkäksi aikaa eteenpäin. Ruotsin säännöstelyn purku osoittautui menestykseksi, koska tuottavuus onollut vakaassa kasvussa ja rautateiden markkinaosuus erityisesti matkustajapuolella on noussut merkittävästi, verrattuna muihin kuljetusmuotoihin. Kuitenkin kilpailua on käytännössä vähän tässä maassa ja parempiatuloksia on lupa odottaa, kun vain säännöstelyn purkaminen jatkuu. Viimeinen tutkimuksemme kohteena oleva maa on Yhdysvallat, joka alistutti rautatiet kilpailulle jo 1980-luvun alussa, käyttäen jo edellä mainittua vertikaalista integraatiota; tämä valinta on taas johtanut hyvin erilaisiin tuloksiin. Vaihtoehtoinen rakenteellinen uudistustapa on suosinut rahtivirtoja matkustajiin nähden, ja lopputuloksena tämä tapaus synnytti yrityksiä huolehtimaan toista näistä kahdesta pääasiakasryhmästä. Viimeaikaiset tulokset tästä yksityistämisprosessista ovat olleet hyviä: jäljellejääneiden yritysten voitot ovat kasvaneet, osinkoja ollaan kyetty jakamaan ja osakkeiden arvostus on noussut. Tässä tutkimusraportissa yritämme kolmen maatapauksen kautta esittää, miten yksityistämisprosessi tulee vaikuttamaan Euroopassa, kun kilpailu rautateillä vapautuu. Me käymmeläpi, mikä näistä kolmesta maaesimerkistä on kaikkein todennäköisin jaesitämme ehdotuksia siihen, miten valtiot voisivat välttää ei-haluttuja sivuvaikutuksia. Kolme maaesimerkkiä, ja lopuksi esitetty lyhyt tilastollinen analyysi osoittavat, että rautateillä on tulevaisuuden potentiaalia Euroopassa, ja kilpailun vapauttaminen on avain tämän potentiaalin realisointiin.

Computational Analysis and Optimization of Real Gas Flow In Small Centrifugal Compressors

Small centrifugal compressors are more and more widely used in many industrialsystems because of their higher efficiency and better off-design performance comparing to piston and scroll compressors as while as higher work coefficient perstage than in axial compressors. Higher efficiency is always the aim of the designer of compressors. In the present work, the influence of four partsof a small centrifugal compressor that compresses heavy molecular weight real gas has been investigated in order to achieve higher efficiency. Two parts concern the impeller: tip clearance and the circumferential position of the splitter blade. The other two parts concern the diffuser: the pinch shape and vane shape. Computational fluid dynamics is applied in this study. The Reynolds averaged Navier-Stokes flow solver Finflo is used. The quasi-steady approach is utilized. Chien's k-e turbulence model is used to model the turbulence. A new practical real gas model is presented in this study. The real gas model is easily generated, accuracy controllable and fairly fast. The numerical results and measurements show good agreement. The influence of tip clearance on the performance of a small compressor is obvious. The pressure ratio and efficiency are decreased as the size of tip clearance is increased, while the total enthalpy rise keeps almost constant. The decrement of the pressure ratio and efficiency is larger at higher mass flow rates and smaller at lower mass flow rates. The flow angles at the inlet and outlet of the impeller are increased as the size of tip clearance is increased. The results of the detailed flow field show that leakingflow is the main reason for the performance drop. The secondary flow region becomes larger as the size of tip clearance is increased and the area of the main flow is compressed. The flow uniformity is then decreased. A detailed study shows that the leaking flow rate is higher near the exit of the impeller than that near the inlet of the impeller. Based on this phenomenon, a new partiallyshrouded impeller is used. The impeller is shrouded near the exit of the impeller. The results show that the flow field near the exit of the impeller is greatly changed by the partially shrouded impeller, and better performance is achievedthan with the unshrouded impeller. The loading distribution on the impeller blade and the flow fields in the impeller is changed by moving the splitter of the impeller in circumferential direction. Moving the splitter slightly to the suction side of the long blade can improve the performance of the compressor. The total enthalpy rise is reduced if only the leading edge of the splitter ismoved to the suction side of the long blade. The performance of the compressor is decreased if the blade is bended from the radius direction at the leading edge of the splitter. The total pressure rise and the enthalpy rise of thecompressor are increased if pinch is used at the diffuser inlet. Among the fivedifferent pinch shape configurations, at design and lower mass flow rates the efficiency of a straight line pinch is the highest, while at higher mass flow rate, the efficiency of a concave pinch is the highest. The sharp corner of the pinch is the main reason for the decrease of efficiency and should be avoided. The variation of the flow angles entering the diffuser in spanwise direction is decreased if pinch is applied. A three-dimensional low solidity twisted vaned diffuser is designed to match the flow angles entering the diffuser. The numerical results show that the pressure recovery in the twisted diffuser is higher than in a conventional low solidity vaned diffuser, which also leads to higher efficiency of the twisted diffuser. Investigation of the detailed flow fields shows that the separation at lower mass flow rate in the twisted diffuser is later than in the conventional low solidity vaned diffuser, which leads to a possible wider flow range of the twisted diffuser.

Data collection and criticality analysis for cost effective maintenance during the life cycle of a flue gas line

Työn tarkoituksena oli kerätä käyttövarmuustietoa savukaasulinjasta kahdelta suomalaiselta sellutehtaalta niiden käyttöönotosta aina tähän päivään asti. Käyttövarmuustieto koostuu luotettavuustiedoista sekä kunnossapitotiedoista. Kerätyn tiedon avulla on mahdollista kuvata tarkasti laitoksen käyttövarmuutta seuraavilla tunnusluvuilla: suunnittelemattomien häiriöiden lukumäärä ja korjausajat, laitteiden seisokkiaika, vikojen todennäköisyys ja korjaavan kunnossapidon kustannukset suhteessa savukaasulinjan korjaavan kunnossapidon kokonaiskustannuksiin. Käyttövarmuustiedon keräysmetodi on esitelty. Savukaasulinjan kriittisten laitteiden määrittelyyn käytetty metodi on yhdistelmä kyselytutkimuksesta ja muunnellusta vian vaikutus- ja kriittisyysanalyysistä. Laitteiden valitsemiskriteerit lopulliseen kriittisyysanalyysiin päätettiin käyttövarmuustietojen sekä kyselytutkimuksen perusteella. Kriittisten laitteiden määrittämisen tarkoitus on löytää savukaasulinjasta ne laitteet, joiden odottamaton vikaantuminen aiheuttaa vakavimmat seuraukset savukaasulinjan luotettavuuteen, tuotantoon, turvallisuuteen, päästöihin ja kustannuksiin. Tiedon avulla rajoitetut kunnossapidon resurssit voidaan suunnata oikein. Kriittisten laitteiden määrittämisen tuloksena todetaan, että kolme kriittisintä laitetta savukaasulinjassa ovat molemmille sellutehtaille yhteisesti: savukaasupuhaltimet, laahakuljettimet sekä ketjukuljettimet. Käyttövarmuustieto osoittaa, että laitteiden luotettavuus on tehdaskohtaista, mutta periaatteessa samat päälinjat voidaan nähdä suunnittelemattomien vikojen todennäköisyyttä esittävissä kuvissa. Kustannukset, jotka esitetään laitteen suunnittelemattomien kunnossapitokustannusten suhteena savukaasulinjan kokonaiskustannuksiin, noudattelevat hyvin pitkälle luotettavuuskäyrää, joka on laskettu laitteen seisokkiajan suhteena käyttötunteihin. Käyttövarmuustiedon keräys yhdistettynä kriittisten laitteiden määrittämiseen mahdollistavat ennakoivan kunnossapidon oikean kohdistamisen ja ajoittamisen laitteiston elinaikana siten, että luotettavuus- ja kustannustehokkuusvaatimukset saavutetaan.

Cuticular and Suberin Polymers of Edible Plants. Analysis by Gas Chromatographic-Mass Spectrometric and Solid State Spectroscopic Methods

Cutin and suberin are structural and protective polymers of plant surfaces. The epidermal cells of the aerial parts of plants are covered with an extracellular cuticular layer, which consists of polyester cutin, highly resistant cutan, cuticular waxes and polysaccharides which link the layer to the epidermal cells. A similar protective layer is formed by a polyaromatic-polyaliphatic biopolymer suberin, which is present particularly in the cell walls of the phellem layer of periderm of the underground parts of plants (e.g. roots and tubers) and the bark of trees. In addition, suberization is also a major factor in wound healing and wound periderm formation regardless of the plants’ tissue. Knowledge of the composition and functions of cuticular and suberin polymers is important for understanding the physiological properties for the plants and for nutritional quality when these plants are consumed as foods. The aims of the practical work were to assess the chemical composition of cuticular polymers of several northern berries and seeds and suberin of two varieties of potatoes. Cutin and suberin were studied as isolated polymers and further after depolymerization as soluble monomers and solid residues. Chemical and enzymatic depolymerization techniques were compared and a new chemical depolymerization method was developed. Gas chromatographic analysis with mass spectrometric detection (GC-MS) was used to assess the monomer compositions. Polymer investigations were conducted with solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (13C CP-MAS NMR), Fourier transform infrared spectroscopy (FTIR) and microscopic analysis. Furthermore, the development of suberin over one year of post-harvest storage was investigated and the cuticular layers from berries grown in the North and South of Finland were compared. The results show that the amounts of isolated cuticular layers and cutin monomers, as well as monomeric compositions vary greatly between the berries. The monomer composition of seeds was found to differ from the corresponding berry peel monomers. The berry cutin monomers were composed mostly of long-chain aliphatic ω-hydroxy acids, with various mid-chain functionalities (double-bonds, epoxy, hydroxy and keto groups). Substituted α,ω-diacids predominated over ω-hydroxy acids in potato suberin monomers and slight differences were found between the varieties. The newly-developed closed tube chemical method was found to be suitable for cutin and suberin analysis and preferred over the solvent-consuming and laborious reflux method. Enzymatic hydrolysis with cutinase was less effective than chemical methanolysis and showed specificity towards α,ω-diacid bonds. According to ₁₃C CP-MAS NMR and FTIR, the depolymerization residues contained significant amounts of aromatic structures, polysaccharides and possible cutan-type aliphatic moieties. Cultivation location seems to have effect on cuticular composition. The materials studied contained significant amounts of different types of biopolymers that could be utilized for several purposes with or without further processing. The importance of the so-called waste material from industrial processes of berries and potatoes as a source of either dietary fiber or specialty chemicals should be further investigated in detail. The evident impact of cuticular and suberin polymers, among other fiber components, on human health should be investigated in clinical trials. These by-product materials may be used as value-added fiber fractions in the food industry and as raw materials for specialty chemicals such as lubricants and emulsifiers, or as building blocks for novel polymers.

Analysis and validation of space averaged drag model for numerical simulations of gas-solid flows in fluidized beds

This thesis presents an approach for formulating and validating a space averaged drag model for coarse mesh simulations of gas-solid flows in fluidized beds using the two-fluid model. Proper modeling for fluid dynamics is central in understanding any industrial multiphase flow. The gas-solid flows in fluidized beds are heterogeneous and usually simulated with the Eulerian description of phases. Such a description requires the usage of fine meshes and small time steps for the proper prediction of its hydrodynamics. Such constraint on the mesh and time step size results in a large number of control volumes and long computational times which are unaffordable for simulations of large scale fluidized beds. If proper closure models are not included, coarse mesh simulations for fluidized beds do not give reasonable results. The coarse mesh simulation fails to resolve the mesoscale structures and results in uniform solids concentration profiles. For a circulating fluidized bed riser, such predicted profiles result in a higher drag force between the gas and solid phase and also overestimated solids mass flux at the outlet. Thus, there is a need to formulate the closure correlations which can accurately predict the hydrodynamics using coarse meshes. This thesis uses the space averaging modeling approach in the formulation of closure models for coarse mesh simulations of the gas-solid flow in fluidized beds using Geldart group B particles. In the analysis of formulating the closure correlation for space averaged drag model, the main parameters for the modeling were found to be the averaging size, solid volume fraction, and distance from the wall. The closure model for the gas-solid drag force was formulated and validated for coarse mesh simulations of the riser, which showed the verification of this modeling approach. Coarse mesh simulations using the corrected drag model resulted in lowered values of solids mass flux. Such an approach is a promising tool in the formulation of appropriate closure models which can be used in coarse mesh simulations of large scale fluidized beds.

The Use of Data Envelopment Analysis as Equity Portfolio Selection Criterion in the Finnish Stock Market

This thesis examines the application of data envelopment analysis as an equity portfolio selection criterion in the Finnish stock market during period 2001-2011. A sample of publicly traded firms in the Helsinki Stock Exchange is examined in this thesis. The sample covers the majority of the publicly traded firms in the Helsinki Stock Exchange. Data envelopment analysis is used to determine the efficiency of firms using a set of input and output financial parameters. The set of financial parameters consist of asset utilization, liquidity, capital structure, growth, valuation and profitability measures. The firms are divided into artificial industry categories, because of the industry-specific nature of the input and output parameters. Comparable portfolios are formed inside the industry category according to the efficiency scores given by the DEA and the performance of the portfolios is evaluated with several measures. The empirical evidence of this thesis suggests that with certain limitations, data envelopment analysis can successfully be used as portfolio selection criterion in the Finnish stock market when the portfolios are rebalanced at annual frequency according to the efficiency scores given by the data envelopment analysis. However, when the portfolios were rebalanced every two or three years, the results are mixed and inconclusive.

Do retail investors use technical analysis? Evidence from Stuttgart stock exchange.

Tutkielma käyttää automaattista kuviontunnistusalgoritmia ja yleisiä kahden liukuvan keskiarvon leikkauspiste –sääntöjä selittääkseen Stuttgartin pörssissä toimivien yksityissijoittajien myynti-osto –epätasapainoa ja siten vastatakseen kysymykseen ”käyttävätkö yksityissijoittajat teknisen analyysin menetelmiä kaupankäyntipäätöstensä perustana?” Perusolettama sijoittajien käyttäytymisestä ja teknisen analyysin tuottavuudesta tehtyjen tutkimusten perusteella oli, että yksityissijoittajat käyttäisivät teknisen analyysin metodeja. Empiirinen tutkimus, jonka aineistona on DAX30 yhtiöiden data vuosilta 2009 – 2013, ei tuottanut riittävän selkeää vastausta tutkimuskysymykseen. Heikko todistusaineisto näyttää kuitenkin osoittavan, että yksityissijoittajat muuttavat kaupankäyntikäyttäytymistänsä eräiden kuvioiden ja leikkauspistesääntöjen ohjastamaan suuntaan.