Studies on membrane properties of cholesterol and 3-beta modified sterol analogs

Cholesterol (Chol) is an important lipid in cellular membranes functioning both as a membrane fluidity regulator, permeability regulator and co-factor for some membrane proteins, e.g. G-protein coupled receptors. It also participates in the formation of signaling platforms and gives the membrane more mechanical strenght to prevent osmotic lysis of the cell. The sterol structure is very conserved and already minor structural modifications can completely abolish its membrane functions. The right interaction with adjacent lipids and the preference of certain lipid structures over others are also key factors in determining the membrane properties of cholesterol. Because of the many important properties of cholesterol it is of value to understand the forces and structural properties that govern the membrane behavior of this sterol. In this thesis we have used established fluorescence spectroscopy methods to study the membrane behavior of both cholesterol and some of its 3β-modified analogs. Using several fluorescent probes we have established how the acyl chain order of the two main lipid species, sphingomyelin (SM) and phosphatidylcholine (PC) affect sterol partitioning as well as characterized the membrane properties of 3β-aminocholesterol and cholesteryl phosphocholine. We concluded that cholesterol prefers SM over PC at equal acyl chain order, indicating that other structural properties besides the acyl chain order are important for sphingomyelin-sterol interactions. A positive charge at the 3β position only caused minor changes in the sterol membrane behavior compared to cholesterol. A large phosphocholine head group caused a disruption in membrane packing together with other membrane lipids with large head groups, but was also able to form stable fluid bilayers together with ceramide and cholesterol. The Ability of the large head group sterol to form bilayers together with ceramide was further explored in the last paper where cholesteryl phosphocholine/ceramide (Chol-PC/Cer) complexes were successfully used to transfer ceramide into cultured cells.

Carte très curieuse de la Mer du Sud, contenant des remarques nouvelles et très utiles non seulement sur les ports et îles de cette mer, mais aussy sur les principaux pays de l'Amérique tant septentrionale que méridionale, avec les noms et la route des voyageurs par qui la découverte en a été faite

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Map of the north coast of Russia indicating the proposed trade route of the Obi-railway

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Developing short sea shipping transportation chains at Helsinki-Tallinn route

Short sea shipping is an important part of the European economy and an alternative to road transport of goods in Europe. It represents an intermodal transport combination of sea and land on a Door-to-Door basis, and it aims to develop more sustainable transport network with the least negative impacts by the transport modes. This Master’s thesis addresses the development of short sea shipping transportation chains at Helsinki-Tallinn route. The Master´s thesis explores the development of short sea shipping at Helsinki-Tallinn route by analyzing the shipping costs per unit transported by different ship types and sizes between port of Helsinki-Vuosaari harbour and port of Tallinn-Muuga harbour, and examining the possibility of Ro-Ro traffic as well. The study is qualitative-quantitative method and it is based on a case study, data is collected from secondary and primary sources, and mixed methods analysis is used to implement the interviews and observations results with the databases analysis. In the thesis factors affecting on short sea shipping are explored and analyzed, also the possibility of Ro-Ro shipping is examined, by comparing the shipping cost and the environmental impact of different ships like container ships, Ropax, and CONRO ships. The finding of this research shows the importance of time at port and utilization as a shipping cost determinants, the relationship between ship type and costing, and the possibility of Ro-Ro shipping.

Genetically Modified Organisms (GMOs) and Agroecology in Agricultural Production in the United States - A Comparative Analysis.

The world’s population is growing at a rapid rate and one of the primary problems of a growing is food supply. To ensure food supply and security, the biggest companies in the agricultural sector of the United States and all over the world have collaborated to produce genetically modified organisms, including crops, that have a tendency to increase yields and are speculated to reduce pesticide use. It’s a technology that is declared to have a multitude of benefits. During the same time period another set of practices has risen to the horizon by the name of agroecology. It spreads across many different sectors such as politics, sociology, environment, health and so on. Moreover, it involves primitive organic techniques that can be applied at farm level to enhance the performance of an ecosystem to effectively decrease the negative effect on environment and health of individuals while producing good quality foods. Since both the processes proclaim sustainable development, a natural question may come in mind that which one seems more favorable? During the course of this study, genetically modified organisms (GMOs) and agroecology are compared within the sphere of social, environmental and health aspects. The results derived upon a comparative analysis of scientific literature tend to prove that GMOs pose a greater threat to the environment, health of individuals and the generalized social balance in the United States compared to agroecological practices. Economic indicators were not included in the study and more studies might be needed in the future to get a broader view on the subject.

Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.

Hävittäjäohjaajan kognitiivisen kuormituksen tason mittaaminen NASA-Task Load Index ja Modified Cooper-Harper -mittareilla F/A-18 virtuaalisimulaattorissa

F/A-18-monitoimihävittäjän ohjaajan tehtävän kognitiiviset vaatimukset ovat korkeat. Kognitiivisen kuormituksen taso vaikuttaa hävittäjäohjaajan suoritustasoon ja subjektiivisiin tun-temuksiin. Yerkesin ja Dodsonin periaatteen mukaisesti erittäin matala tai erittäin korkea kuormituksen taso laskee suoritustasoa. Optimaalinen kuormituksen taso ja suoritustaso saa-vutetaan jossain ääripäiden välillä. Hävittäjäohjaajan kognitiivisen kuormituksen tasoon vaikuttaa lentotehtävän suorittamiseen vaadittava henkinen ponnistelu. Vaadittavan ponnistelun taso riippuu tehtävien vaatimustasosta ja määrästä, tehtäviin käytettävissä olevasta ajasta sekä yksilöllisistä ominaisuuksista. Tutkimuksessa mitattiin kognitiivisen kuormituksen tasoa subjektiivisen arvioinnin menetelmällä NASA-TLX (National Aeronautics and Space Administration - Task Load Index) ja MCH (Modified Cooper-Harper) -mittareilla. Tutkimuksessa selvitettiin mittareiden havaintoarvojen muutosta, sensitiivisyyttä ja yhdenmukaisuutta kognitiivisen kuormituksen tason muuttuessa. Tutkimuksen mittauksiin osallistui 35 Suomen ilmavoimien aktiivisessa palveluksessa olevaa F/A-18-monitoimihävittäjäohjaajaa. Koehenkilöiden lentotuntien keskiarvo F/A-18-monitoimihävittäjällä oli 598 tuntia ja keskihajonta 445 tuntia. Koehenkilöiden tehtävänä oli lentää F/A-18-virtuaalisimulaattorilla 11 ILS (Instrument Landing System) -mittarilähestymistä eri aloitusetäisyyksiltä kiitotien kynnyksestä. Kognitiivisesti kuormitta-van mittarilähestymistehtävän aikana kuormituksen tasoa nostettiin lisätehtävillä ja vähentä-mällä tehtäviin käytettävissä olevaa aikaa. Koehenkilöitä pyydettiin ponnistelemaan mahdollisimman paljon tehtävien suorittamisen aikana hyvän suoritustason ylläpitämiseksi. Tulosten perusteella mittareiden havaintoarvot muuttuivat kognitiivisen kuormituksen tason muuttuessa. Käytettävissä olevan ajan vaikutus kognitiivisen kuormituksen tasoon oli tilastollisesti erittäin merkitsevä. Mittarit olivat sensitiivisiä kognitiivisen kuormituksen tason muutokselle ja antoivat yhdenmukaisia havaintoarvoja.

Analytics for the modified kraft pulps

Tämän diplomityön tavoitteena on kehittää sopiva analyyttinen menetelmä muokatun kraft-sellukuidun substituutioasteen (DS) kvantitatiivista määrittämistä varten. Muokkauksella tarkoitetaan tässä yhteydessä joko kovalenttisesti tai adsorption avulla tapahtuvaa molekyylin kiinnittymistä sellukuidun pinnalle. Työn kirjallisuusosuudessa käsitellään lyhyesti eri muokkaustapoja ja yhdisteitä joiden avulla voidaan saavuttaa haluttuja ominaisuuksia sellusta valmistetuille lopputuotteille. Lisäksi kirjallisuusosuudessa käydään läpi käyttötarkoitukseen soveltuvimpia suoria ja epäsuoria analyysimenetelmiä. Analyysimenetelmistä kaikkein lupaavimpia testattiin työn kokeellisessa osassa. Diplomityön kokeellisessa osassa keskityttiin kehittämään muokatulle sellulle kvantitatiivista menetelmää DS:n määrittämiseksi Fourier-muunnos infrapuna-vaimennettu kokonaisheijastus (FTIR-ATR) spektrometrillä. Kirjallisuuskatsauksessa ei löytynyt yhtään dokumentoitua tutkimusta, jossa FTIR-ATR menetelmää olisi käytetty muokatun sellukuidun kvantitatiiviseen tutkimukseen. Muiden analyysimenetelmien, kuten alkuaineanalyysin, termogravimetrisen analyysin (TGA) ja valomikroskopian avulla pyrittiin tuottamaan lisätietoa muokkauksesta. Kvantitatiivisen FTIR-ATR menetelmän kehitykseen käytetyt muokatut sellukuidut olivat selluloosa-asetaattia ja selluloosa betainaattia. Saatujen tulosten perusteella muokattujen sulfiitti- ja kraft sellukuitujen DS:n kvantitatiivinen määrittäminen on mahdollista FTIR-ATR menetelmällä. Vähäinen kalibrointipisteiden määrä vaikeutti tarkan analyysimenetelmän tekemistä. Kehitetyn menetelmän suurimpina ongelmina olivat kiinteiden näytteiden heterogeenisyys sekä mahdollisten epäpuhtauksien tunnistaminen. Jatkotutkimusten avulla kehitettyä menetelmää on kuitenkin mahdollista käyttää muokattujen sellukuitujen jatkuvaan analysointiin selluteollisuudessa.

A modified nominal stress method for fatigue assessment of steel plates with thermally cut edges

Thermal cutting methods, are commonly used in the manufacture of metal parts. Thermal cutting processes separate materials by using heat. The process can be done with or without a stream of cutting oxygen. Common processes are Oxygen, plasma and laser cutting. It depends on the application and material which cutting method is used. Numerically-controlled thermal cutting is a cost-effective way of prefabricating components. One design aim is to minimize the number of work steps in order to increase competitiveness. This has resulted in the holes and openings in plate parts manufactured today being made using thermal cutting methods. This is a problem from the fatigue life perspective because there is local detail in the as-welded state that causes a rise in stress in a local area of the plate. In a case where the static utilization of a net section is full used, the calculated linear local stresses and stress ranges are often over 2 times the material yield strength. The shakedown criteria are exceeded. Fatigue life assessment of flame-cut details is commonly based on the nominal stress method. For welded details, design standards and instructions provide more accurate and flexible methods, e.g. a hot-spot method, but these methods are not universally applied to flame cut edges. Some of the fatigue tests of flame cut edges in the laboratory indicated that fatigue life estimations based on the standard nominal stress method can give quite a conservative fatigue life estimate in cases where a high notch factor was present. This is an undesirable phenomenon and it limits the potential for minimizing structure size and total costs. A new calculation method is introduced to improve the accuracy of the theoretical fatigue life prediction method of a flame cut edge with a high stress concentration factor. Simple equations were derived by using laboratory fatigue test results, which are published in this work. The proposed method is called the modified FAT method (FATmod). The method takes into account the residual stress state, surface quality, material strength class and true stress ratio in the critical place.