Kromatografisen erotusfaasin huokoskoon karakterisointi

Työssä tutkittiin sulfonoitujen polystyreenidivinyylibentseenirunkoisten geeli-, meso- ja makrohuokoistenioninvaihtohartsien rakennetta käyttäen useita eri karakterisointimenetelmiä. Lisäksi työssä tutkittiin hartsien huokoskoon vaikutusta aminohappojen kromatografisessa erotuksessa. Työn pääpaino oli hartsien huokoskoon ja huokoisuuden määrittämisessä. Sen selvittämiseksi käytettiin hyväksi elektronimikroskopiaa, typpiadsorptiomittauksia, sekä käänteistä kokoekskluusiokromatografiaa. Parhaat tulokset saatiin käänteisellä kokoekskluusiokromatografialla, joka perustuu erikokoisten dekstraanipolymeerien käyttöön mallimolekyyleinä. Menetelmä sopii meso- ja makrohuokoisuuden tutkimiseen, mutta sen heikkoutena on erittäin pitkä mittausaika. Menetelmä antaa myös huokoskokojakauman, mutta yhden hartsin mittaaminen voi kestää viikon. Menetelmää muutettiin siten, että käytettiin määritettävää huokoskokoaluetta kuvaavien kahden dekstraanipolymeerin seosta. Kromatografiset ajo-olosuhteet optimoitiin sellaisiksi, että injektoidussa seoksessa olevien dekstraanien vastehuiput erottuivat toisistaan. Tällöin voitiin luotettavasti määrittää tutkittavan stationaarifaasin suhteellinen huokoisuus. Tätä työssä kehitettyä nopeaa käänteiseen kokoekskluusiokromatografiaan perustuvaa menetelmää kutsutaan kaksipistemenetelmäksi. Hartsien sulfonihapporyhmien määrää ja jakautumista tutkittiin määrittämällä hartsien kationinvaihtokapasiteetti sekä tutkimalla hartsin pintaa konfokaali-Raman-spektroskopian avulla. Sulfonihapporyhmien ioninvaihtokyvyn selvittämiseksi mitattiin K+-muotoon muutetusta hartsista S/K-suhde poikkileikkauspinnasta. Tulosten perusteella hartsit olivat tasaisesti sulfonoituneet ja 95 % rikkiatomeista oli toimivassa ioninvaihtoryhmässä. Aminohappojen erotuksessa malliaineina oli lysiini, seriini ja tryptofaani. Hartsi oli NH4+-muodossa ja petitilavuus oli 91 mL. Eluenttina käytettiin vettä, jonka pH oli 10. Paras tulos saatiin virtausnopeudella 0,1 mL/min, jolla kaikki kolme aminohappoa erottuivat toisistaan Finex Oy:n mesohuokoisella KEF78-hartsilla. Muilla tutkituilla hartseilla kaikki kolme aminohappoa eivät missään ajo-olosuhteissa erottuneet täysin.

Characterisation of pigment particles by scanning electron microscope and image analysis programs

Coating and filler pigments have strong influence to the properties of the paper. Filler content can be even over 30 % and pigment content in coating is about 85-95 weight percent. The physical and chemical properties of the pigments are different and the knowledge of these properties is important for optimising of optical and printing properties of the paper. The size and shape of pigment particles can be measured by different analysers which can be based on sedimentation, laser diffraction, changes in electric field etc. In this master's thesis was researched particle properties especially by scanning electron microscope (SEM) and image analysis programs. Research included nine pigments with different particle size and shape. Pigments were analysed by two image analysis programs (INCA Feature and Poikki), Coulter LS230 (laser diffraction) and SediGraph 5100 (sedimentation). The results were compared to perceive the effect of particle shape to the performance of the analysers. Only image analysis programs gave parameters of the particle shape. One part of research was also the sample preparation for SEM. Individual particles should be separated and distinct in ideal sample. Analysing methods gave different results but results from image analysis programs corresponded even to sedimentation or to laser diffraction depending on the particle shape. Detailed analysis of the particle shape required high magnification in SEM, but measured parameters described very well the shape of the particles. Large particles (ecd~1 µm) could be used also in 3D-modelling which enabled the measurement of the thickness of the particles. Scanning electron microscope and image analysis programs were effective and multifunctional tools for particle analyses. Development and experience will devise the usability of analysing method in routine use.

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Three Wavelength Optical Probe for Surface Roughness Measurements of Paper Samples

In the present diploma work optical inspection methods were used to investigate surface roughness of paper samples. A special measurement setup, which includes three laser light sources of three different wavelengths, photodetector and goniometer, was used to measure the reflected laser light properties. The intensity of the light reflected in specular direction was measured versus the laser incidence angle for reference metal sample. The value of roughness was estimated and compared to initially known value of metal sample roughness. Thus, the measurement equipment and method were validated. Then the reflected intensity was measured versus reflection angle at constant incidence angle for the same metal sample and paper samples under investigation. The final values of the surface roughness were obtained from the analysis of the reflected intensity dependence. The results are in good correlation with other research groups.

Electric field calibration method for scanning electron microscope

This paper proposes a calibration method which can be utilized for the analysis of SEM images. The field of application of the developed method is a calculation of surface potential distribution of biased silicon edgeless detector. The suggested processing of the data collected by SEM consists of several stages and takes into account different aspects affecting the SEM image. The calibration method doesn’t pretend to be precise but at the same time it gives the basics of potential distribution when the different biasing voltages applied to the detector.

Electric field measurements using scanning electron microscope

The main idea of this diploma work is to study electric field distribution on the micro level. For this purpose a silicon edgeless detector was chosen as the object of investigation and scanning electron microscope as an investigation tool. Silicon edgeless detector is an important part of installation for studying proton-proton interactions in TOTEM experiment at Large Hadron Collider. For measurement of electric field distribution inside scanning electron microscope a voltage contrast method was applied.

Leaf-Targeted Ferredoxin-NADP+-Oxidoreductase (FNR): Electron Transfer Properties and Thylakoid Association in Arabidopsis thaliana

Photosynthetic reactions are divided in two parts: light-driven electron transfer reactions and carbon fixation reactions. Electron transfer reactions capture solar energy and split water molecules to form reducing energy (NADPH) and energy-carrying molecules (ATP). These end-products are used for fixation of inorganic carbon dioxide into organic sugar molecules. Ferredoxin-NADP⁺ oxidoreductase (FNR) is an enzyme that acts at the branch point between the electron transfer reactions and reductive metabolism by catalyzing reduction of NADP+ at the last step of the electron transfer chain. In this thesis, two isoforms of FNR from A rabidopsis thaliana, FNR1 and FNR2, were characterized using the reverse genetics approach. The fnr1 and fnr2 mutant plants resembled each other in many respects. Downregulation of photosynthesis protected the single fnr mutant plants from excess formation of reactive oxygen species (ROS), even without significant upregulation of antioxidative mechanisms. Adverse growth conditions, however, resulted in phenotypic differences between fnr1 and fnr2. While fnr2 plants showed downregulation of photosynthetic complexes and upregulation of antioxidative mechanisms under low-temperature growth conditions, fnr1 plants had the wild-type phenotype, indicating that FNR2 may have a specific role in redistribution of electrons under unfavorable conditions. The heterozygotic double mutant (fnr1xfnr2) was severely devoid of chloroplastic FNR, which clearly restricted photosynthesis. The fnr1xfnr2 plants used several photoprotective mechanisms to avoid oxidative stress. In wild-type chloroplasts, both FNR isoforms were found from the stroma, the thylakoid membrane, and the inner envelope membrane. In the absence of the FNR1 isoform, FNR2 was found only in the stroma, suggesting that FNR1 and FNR2 form a dimer, by which FNR1 anchors FNR2 to the thylakoid membrane. Structural modeling predicted formation of an FNR dimer in complex with ferredoxin. In this thesis work, Tic62 was found to be the main protein that binds FNR to the thylakoid membrane, where Tic62 and FNR formed high molecular weight complexes. The formation of such complexes was shown to be regulated by the redox state of the chloroplast. The accumulation of Tic62-FNR complexes in darkness and dissociation of complexes from the membranes in light provide evidence that the complexes may have roles unrelated to photosynthesis. This and the high viability of fnr1 mutant plants lacking thylakoid-bound FNR indicate that the stromal pool of FNR is photosynthetically active.

Charge transport in disordered materials : simulations, theory, and numerical modeling of hopping transport and electron-hole recombination

Min avhandling behandlar hur oordnade material leder elektrisk ström. Bland materialen som studeras finns ledande polymerer, d.v.s. plaster som leder ström, och mer allmänt organiska halvledare. Av de här materialen har man kunnat bygga elektroniska komponenter, och man hoppas på att kunna trycka hela kretsar av organiska material. För de här tillämpningarna är det viktigt att förstå hur materialen själva leder elektrisk ström. Termen oordnade material syftar på material som saknar kristallstruktur. Oordningen gör att elektronernas tillstånd blir lokaliserade i rummet, så att en elektron i ett visst tillstånd är begränsad t.ex. till en molekyl eller ett segment av en polymer. Det här kan jämföras med kristallina material, där ett elektrontillstånd är utspritt över hela kristallen (men i stället har en väldefinierad rörelsemängd). Elektronerna (eller hålen) i det oordnade materialet kan röra sig genom att tunnelera mellan de lokaliserade tillstånden. Utgående från egenskaperna för den här tunneleringsprocessen, kan man bestämma transportegenskaperna för hela materialet. Det här är utgångspunkten för den så kallade hopptransportmodellen, som jag har använt mig av. Hopptransportmodellen innehåller flera drastiska förenklingar. Till exempel betraktas elektrontillstånden som punktformiga, så att tunneleringssannolikheten mellan två tillstånd endast beror på avståndet mellan dem, och inte på deras relativa orientation. En annan förenkling är att behandla det kvantmekaniska tunneleringsproblemet som en klassisk process, en slumpvandring. Trots de här grova approximationerna visar hopptransportmodellen ändå många av de fenomen som uppträder i de verkliga materialen som man vill modellera. Man kan kanske säga att hopptransportmodellen är den enklaste modell för oordnade material som fortfarande är intressant att studera. Man har inte hittat exakta analytiska lösningar för hopptransportmodellen, därför använder man approximationer och numeriska metoder, ofta i form av datorberäkningar. Vi har använt både analytiska metoder och numeriska beräkningar för att studera olika aspekter av hopptransportmodellen. En viktig del av artiklarna som min avhandling baserar sig på är att jämföra analytiska och numeriska resultat. Min andel av arbetet har främst varit att utveckla de numeriska metoderna och applicera dem på hopptransportmodellen. Därför fokuserar jag på den här delen av arbetet i avhandlingens introduktionsdel. Ett sätt att studera hopptransportmodellen numeriskt är att direkt utföra en slumpvandringsprocess med ett datorprogram. Genom att föra statisik över slumpvandringen kan man beräkna olika transportegenskaper i modellen. Det här är en så kallad Monte Carlo-metod, eftersom själva beräkningen är en slumpmässig process. I stället för att följa rörelsebanan för enskilda elektroner, kan man beräkna sannolikheten vid jämvikt för att hitta en elektron i olika tillstånd. Man ställer upp ett system av ekvationer, som relaterar sannolikheterna för att hitta elektronen i olika tillstånd i systemet med flödet, strömmen, mellan de olika tillstånden. Genom att lösa ekvationssystemet fås sannolikhetsfördelningen för elektronerna. Från sannolikhetsfördelningen kan sedan strömmen och materialets transportegenskaper beräknas. En aspekt av hopptransportmodellen som vi studerat är elektronernas diffusion, d.v.s. deras slumpmässiga rörelse. Om man betraktar en samling elektroner, så sprider den med tiden ut sig över ett större område. Det är känt att diffusionshastigheten beror av elfältet, så att elektronerna sprider sig fortare om de påverkas av ett elektriskt fält. Vi har undersökt den här processen, och visat att beteendet är väldigt olika i endimensionella system, jämfört med två- och tredimensionella. I två och tre dimensioner beror diffusionskoefficienten kvadratiskt av elfältet, medan beroendet i en dimension är linjärt. En annan aspekt vi studerat är negativ differentiell konduktivitet, d.v.s. att strömmen i ett material minskar då man ökar spänningen över det. Eftersom det här fenomenet har uppmätts i organiska minnesceller, ville vi undersöka om fenomenet också kan uppstå i hopptransportmodellen. Det visade sig att det i modellen finns två olika mekanismer som kan ge upphov till negativ differentiell konduktivitet. Dels kan elektronerna fastna i fällor, återvändsgränder i systemet, som är sådana att det är svårare att ta sig ur dem då elfältet är stort. Då kan elektronernas medelhastighet och därmed strömmen i materialet minska med ökande elfält. Elektrisk växelverkan mellan elektronerna kan också leda till samma beteende, genom en så kallad coulombblockad. En coulombblockad kan uppstå om antalet ledningselektroner i materialet ökar med ökande spänning. Elektronerna repellerar varandra och ett större antal elektroner kan leda till att transporten blir långsammare, d.v.s. att strömmen minskar.

Meriteollisuuden talouden ja suhdanteiden kehitys 2006–2020 – FIMECC Probe -hankkeen toimialakatsaus 2012

Tämä Fimecc Innovations & Network -ohjelman PROBE-tutkimushankkeessa tehty raportti sisältää vuosittaisen katsauksen suomalaisten meriteollisuusyritysten taloudelliseen tilaan, markkinoiden kehitykseen sekä suhdanneodotuksiin. Talouden osalta raportti sisältää meriteollisuuden kokonaisvolyymin kehityksen arvioinnin, kasvun ja kannattavuuden seurannan toimijaryhmätasolla 2006–2011 sekä ennakkotietoja vuoden 2012 taloudellisesta kehityksestä (vuoden 2012 viralliset tilinpäätöstiedot ovat kattavasti saatavilla vasta loppuvuonna 2013). Talousosiossa on samalla pyritty arvioimaan yritysten aikaisempina vuosina tekemiä suhdanneodotuksia toteutuneeseen taloudelliseen tilanteeseen. Markkinasegmenttien tilannetta raportissa tarkastellaan kahden markkinan osalta: risteily- sekä ro-ro ja ro-pax -markkinoilla. Raportin kolmas osa tarkastelee yritysten suhdannenäkymiä vuodelle 2013 perustuen syksyn 2012 tilanteeseen. Osa sisältää myös erityisteeman Suomen koko meriteollisuuden kehityskuvasta vuodelle 2020, jossa yritykset arvioivat mm. alan tulevaisuuden vetureita, uhkia ja mahdollisuuksia sekä tarvittavia toimenpiteitä alan menestymiseksi tulevaisuudessa.

Kelvin Probe Force Microscopy (KPFM) characterization of lanthanum lutetium oxide high-k dielectric thin films

Lanthanum lutetium oxide (LaLuO3) thin films were investigated considering their perspective application for industrial microelectronics. Scanning probe microscopy (SPM) techniques permitted to visualize the surface topography and study the electric properties. This work compared both the material properties (charge behavior for samples of 6 nm and 25 nm width) and the applied SPM modes. Particularly, Kelvin probe force microscopy (KPFM) was applied to characterize local potential difference with high lateral resolution. Measurements showed the difference in morphology, chargeability and charge dissipation time for both samples. The polarity effect was detected for this material for the first time. Lateral spreading of the charged spots indicate the diffusive mechanism to be predominant in charge dissipation. This allowed to estimate the diffusion coefficient and mobility. Using simple electrostatic model it was found that charge is partly leaking into the interface oxide layer.

Readout Electronics for Gas Electron Multiplier Detectors

The European Organization for Nuclear Research (CERN) operates the largest particle collider in the world. This particle collider is called the Large Hadron Collider (LHC) and it will undergo a maintenance break sometime in 2017 or 2018. During the break, the particle detectors, which operate around the particle collider, will be serviced and upgraded. Following the improvement in performance of the particle collider, the requirements for the detector electronics will be more demanding. In particular, the high amount of radiation during the operation of the particle collider sets requirements for the electronics that are uncommon in commercial electronics. Electronics that are built to function in the challenging environment of the collider have been designed at CERN. In order to meet the future challenges of data transmission, a GigaBit Transceiver data transmission module and an E-Link data bus have been developed. The next generation of readout electronics is designed to benefit from these technologies. However, the current readout electronics chips are not compatible with these technologies. As a result, in addition to new Gas Electron Multiplier (GEM) detectors and other technology, a new compatible chip is developed to function within the GEMs for the Compact Muon Solenoid (CMS) project. In this thesis, the objective was to study a data transmission interface that will be located on the readout chip between the E-Link bus and the control logic of the chip. The function of the module is to handle data transmission between the chip and the E-Link. In the study, a model of the interface was implemented with the Verilog hardware description language. This process was simulated by using chip design software by Cadence. State machines and operating principles with alternative possibilities for implementation are introduced in the E-Link interface design procedure. The functionality of the designed logic is demonstrated in simulation results, in which the implemented model is proven to be suitable for its task. Finally, suggestions that should be considered for improving the design have been presented.

Regulation of photosynthetic electron transfer in plant chloroplasts

This thesis focuses on the molecular mechanisms regulating the photosynthetic electron transfer reactions upon changes in light intensity. To investigate these mechanisms, I used mutants of the model plant Arabidopsis thaliana impaired in various aspects of regulation of the photosynthetic light reactions. These included mutants of photosystem II (PSII) and light harvesting complex II (LHCII) phosphorylation (stn7 and stn8), mutants of energy-dependent non-photochemical quenching (NPQ) (npq1 and npq4) and of regulation of photosynthetic electron transfer (pgr5). All of these processes have been extensively investigated during the past decades, mainly on plants growing under steady-state conditions, and therefore many aspects of acclimation processes may have been neglected. In this study, plants were grown under fluctuating light, i.e. the alternation of low and high intensities of light, in order to maximally challenge the photosynthetic regulatory mechanisms. In pgr5 and stn7 mutants, the growth in fluctuating light condition mainly damaged PSI while PSII was rather unaffected. It is shown that the PGR5 protein regulates the linear electron transfer: it is essential for the induction of transthylakoid ΔpH that, in turn, activates energy-dependent NPQ and downregulates the activity of cytochrome b6f. This regulation was shown to be essential for the photoprotection of PSI under fluctuations in light intensity. The stn7 mutants were able to acclimate under constant growth light conditions by modulating the PSII/PSI ratio, while under fluctuating growth light they failed in implementing this acclimation strategy. LHCII phosphorylation ensures the balance of the excitation energy distribution between PSII and PSI by increasing the probability for excitons to be trapped by PSI. LHCII can be phosphorylated over all of the thylakoid membrane (grana cores as well as stroma lamellae) and when phosphorylated it constitutes a common antenna for PSII and PSI. Moreover, LHCII was shown to work as a functional bridge that allows the energy transfer between PSII units in grana cores and between PSII and PSI centers in grana margins. Consequently, PSI can function as a quencher of excitation energy. Eventually, the LHCII phosphorylation, NPQ and the photosynthetic control of linear electron transfer via cytochrome b6f work in concert to maintain the redox poise of the electron transfer chain. This is a prerequisite for successful plant growth upon changing natural light conditions, both in short- and long-term.

Reducing contact resistance in graphene devices

In this thesis, the contact resistance of graphene devices was investigated because high contact resistance is detrimental to the performance of graphene field-effect transistors (GFET). Method for increasing so-called edge-contact area was applied in device fabrication process, as few nanometers thick Ni layer was used as a catalytic etchant during the annealing process. Finally, Ni was also used as a metal for contact. GFETs were fabricated using electron beam lithography using graphene fabricated by chemical vapor deposition (CVD). Critical part of the fabrication process was to preserve the high quality of the graphene channel while etching the graphene at contact areas with Ni during the annealing. This was achieved by optimizing the combination of temperature and gas flows. The structural properties of graphene were studied using scanning electron microscopy, scanning confocal μ-Raman spectroscopy and optical microscopy. Evaluation of electric transport properties including contact resistance was carried out by transmission line method and four-probe method. The lowest contact resistance found was about at 350 Ωμm. In addition, different methods to transfer CVD graphene synthesized on copper were studied. Typical method using PMMA as a supporting layer leaves some residues after its removal, thus effecting on the performance of a graphene devices. In a metal assisted transfer method, metal is used as an interfacial layer between PMMA and graphene. This allows more effective removal of PMMA. However, Raman spectra of graphene transferred by metal assisted method showed somewhat lower quality than the PMMA assisted method

Modeling Front End Electronics for a Gas Electron Multiplier Detector

The Large Hadron Collider (LHC) in The European Organization for Nuclear Research (CERN) will have a Long Shutdown sometime during 2017 or 2018. During this time there will be maintenance and a possibility to install new detectors. After the shutdown the LHC will have a higher luminosity. A promising new type of detector for this high luminosity phase is a Triple-GEM detector. During the shutdown these detectors will be installed at the Compact Muon Solenoid (CMS) experiment. The Triple-GEM detectors are now being developed at CERN and alongside also a readout ASIC chip for the detector. In this thesis a simulation model was developed for the ASICs analog front end. The model will help to carry out more extensive simulations and also simulate the whole chip before the whole design is finished. The proper functioning of the model was tested with simulations, which are also presented in the thesis.