Uusi transatlanttinen turvallisuusyhteisö : EU:n nousu transatlanttisissa suhteissa

Only abstract. Paper copies of master’s theses are listed in the Helka database (http://www.helsinki.fi/helka). Electronic copies of master’s theses are either available as open access or only on thesis terminals in the Helsinki University Library.Vain tiivistelmä. Sidottujen gradujen saatavuuden voit tarkistaa Helka-tietokannasta (http://www.helsinki.fi/helka). Digitaaliset gradut voivat olla luettavissa avoimesti verkossa tai rajoitetusti kirjaston opinnäytekioskeilla.Endast sammandrag. Inbundna avhandlingar kan sökas i Helka-databasen (http://www.helsinki.fi/helka). Elektroniska kopior av avhandlingar finns antingen öppet på nätet eller endast tillgängliga i bibliotekets avhandlingsterminaler.Tämä tutkielma tarkastelee transatlanttisten suhteiden muutosta kylmän sodan jälkeen. Tarkastelun painopiste on Euroopan unionin (EU) nousevassa asemassa suhteessa Yhdysvaltoihin. Tutkimusongelma painottuu oletettuun kriisiin EU:n ja Yhdysvaltojen välillä. Päätutkimuskohteena on EU:n nouseva turvallisuus- ja puolustuspoliittinen asema ja sen aiheuttamat muutokset transatlanttisissa suhteissa. Transatlanttiset suhteet on rajattu koskemaan ainoastaan turvallisuuspoliittisia kysymyksiä. Painopiste on erityisesti sotilaallisessa turvallisuudessa. Teoreettinen viitekehys perustuu Karl W. Deutschin vuonna 1957 muotoilemaan teoriaan turvallisuusyhteisöistä. Tätä teoriaa täydennetään Emmanuel Adlerin ja Michael Barnettin näkemyksillä turvallisuusyhteisöistä. Tutkimuksen perusteella tullaan siihen lopputulokseen, että huolimatta turvallisuusyhteisön sisällä kytevästä kriisistä, on löydettävissä enemmän yhteisöä ylläpitäviä voimia kuin sitä hajottavia. Tutkimuksessa tarkastellaan kylmän sodan päättymisen jälkeen turvallisuusyhteisölle ilmenneitä ongelmia. Painotus tutkimuksessa on Irakin sodan jälkeiseen aikaan. Loppupäätelminä todetaan, että keskinäinen dialogi ja sen lisääminen on yksi merkittävistä luottamusta herättävistä seikoista transatlanttisen turvallisuusyhteisön sisällä. Vahvoina yhteisöä koossapitävinä voimina toimivat yhteiset arvot, pitkän aikavälin intressit kansainvälisen politiikan kentällä sekä halu ratkaista keskinäiset ongelmat rauhanomaisesti

VIRANOMAISEN VALITUSOIKEUS

Tämä työ on jatkoa kandidaatin tutkinnolleni. Työn tarkoitus on antaa lukijalle yleiskuva siitä, mitä hallintolainkäyttölain 6.2 § mukainen viranomaisen valitusoikeus tarkoittaa. Tämän työn kantavat tut-kimuskysymykset ovat: Mitä tarkoittaa viranomaisen valitusoikeus? Milloin viranomaisella on valitus-oikeus? Mitä viranomaisen valitusoikeudella halutaan saavuttaa? Tutkielman pääasiallinen tutkimusmenetelmä on oikeusdogmatiikka. Tutkimus tarkastelee edellä mai-nittuja tutkimuskysymyksiä lainsäädäntöä, lain esitöitä ja oikeuskäytäntöä hyödyntäen. Tutkielma on jaettu niin, että ensin työssä käsitellään valitusoikeuden yleistä asemaa ja tehtävää. Tä-män jälkeen viranomaisen valitusoikeutta yleislain pohjalta ja viimeisessä luvussa käsitellään viran-omaisen valitusoikeutta erityislainsäädännön näkökulmasta. Tutkimus tarkastelee viranomaisen asemaa ja sitä mikä on viranomaisen valitusoikeuden asema yksilön oikeusturvaan peilattuna. Työn tarkoitus on tuoda esiin niin negatiivisia ja positiivisia vaikutuksia vi-ranomaisen valitusoikeudesta. Vertaan tutkimuksessa viranomaisen asemaa ja valitusoikeutta myös Ruotsiin. Tutkielmassa käsittelen myös, kenellä viranomaisella on valitusoikeus ja pitäisikö tätä vali-tusoikeutta käyttää vain viranomaisen päätöksenteosta erillinen viranomainen. Tutkielmassa käsitellään myös viranomaisen valitusoikeuden muutostarpeita. Viranomaisen valitusoi-keuden määräytymisperusteita pitäisi selventää. Viranomaisen valitusoikeus on toimiva valvonnan väline. Valitusoikeuden käytössä pitäisi pitää huoli siitä, että valitusoikeutta käytetään mahdollisimman objektiivisesti.fi=Opinnäytetyö kokotekstinä PDF-muodossa.|en=Thesis fulltext in PDF format.|sv=Lärdomsprov tillgängligt som fulltext i PDF-format

Parahydrogen-Induced Polarization in Hydrogenation Reactions Mediated by a Metal-Free Catalyst

We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal-free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non-pairwise mechanism of H-2 transfer to alkynes that normally prevents parahydrogen-induced polarization (PHIP) from being observed. Nevertheless, the specific spin dynamics in catalytic intermediates leads to the hyperpolarization of predominantly one hydrogen in alkene. PHIP enabled the detection of important HCAT-alkyne-H-2 intermediates through substantial H-1, B-11 and N-15 signal enhancement and allowed advanced characterization of the catalytic process.Peer reviewe

High-throughput continuous-flow system for SABRE hyperpolarization

Signal Amplification By Reversible Exchange (SABRE) is a versatile method for hyperpolarizing small organic molecules that helps to overcome the inherent low signal-to-noise ratio of nuclear magnetic resonance (NMR) measurements. It offers orders of magnitude enhanced signal strength, but the obtained nuclear polarization usually rapidly relaxes, requiring a quick transport of the sample to the spectrometer. Here we report a new design of a polarizing system, which can be used to prepare a continuous flow of SABRE-hyperpolarized sample with a considerable throughput of several millilitres per second and a rapid delivery into an NMR instrument. The polarizer performance under different conditions such as flow rate of the hydrogen or liquid sample is tested by measuring a series of NMR spectra and magnetic resonance images (MRI) of hyperpolarized pyridine in methanol. Results show a capability to continuously produce sample with dramatically enhanced signal over two orders of magnitude. The constant supply of hyperpolarized sample can be exploited, e.g., in experiments requiring multiple repetitions, such as 2D- and 3D-NMR or MRI measurements, and also naturally allows measurements of flow maps, including systems with high flow rates, for which the level of achievable thermal polarization might not be usable any more. In addition, the experiments can be viably carried out in a non-deuterated solvent, due to the effective suppression of the thermal polarization by the fast sample flow. The presented system opens the possibilities for SABRE experiments requiring a long-term, stable and high level of nuclear polarization

Ultrafast multidimensional Laplace NMR for a rapid and sensitive chemical analysis

Traditional nuclear magnetic resonance (NMR) spectroscopy relies on the versatile chemical information conveyed by spectra. To complement conventional NMR, Laplace NMR explores diffusion and relaxation phenomena to reveal details on molecular motions. Under a broad concept of ultrafast multidimensional Laplace NMR, here we introduce an ultrafast diffusion-relaxation correlation experiment enhancing the resolution and information content of corresponding 1D experiments as well as reducing the experiment time by one to two orders of magnitude or more as compared with its conventional 2D counterpart. We demonstrate that the method allows one to distinguish identical molecules in different physical environments and provides chemical resolution missing in NMR spectra. Although the sensitivity of the new method is reduced due to spatial encoding, the single-scan approach enables one to use hyperpolarized substances to boost the sensitivity by several orders of magnitude, significantly enhancing the overall sensitivity of multidimensional Laplace NMR

Quantifying the Diffusion of a Fluid through Membranes by RemoteDetection MRI

We present a method to measure self-diffusion acrossmembranes without the need for concentration or pressure gradients.Hyperpolarized xenon in combination with remote detection of NMR allowsthe measurement of membrane permeation, even in the gas phase. Theresulting images allow quantification of the amount of fluid diffusedthrough the membrane, and represent an alternative, potentially moreprecise way of measuring a membrane diffusion coefficient. The use ofremote detection of NMR allows for non-invasive signal encoding coupledto sensitive detection, making this approach ideal for the study ofdiffusion in intact devices such as fuel cells or separationsystems

Effect of natural weathering on water absorption and pore size distribution in thermally modified wood determined by nuclear magnetic resonance

Funder: Teollisuusneuvos Heikki Väänänen's FundFunder: International Thermowood AssociationFunder: Quantum Institute, University of OuluAbstractThermally modified wood (TMW) is widely used in outdoor applications due to its advanced properties towards weathering stresses. Although the structure changes of TMW from weather factors have been reported, investigation of the quantitative analysis of water states and cell wall structure of TMW after weathering is limited. In this work, the amount of bound water, fiber saturation point (FSP), cell wall pores, and free water distribution of thermally modified Scots pine, Norway spruce, and European ash were measured before and after a 2-year natural weathering via NMR relaxometry, cryoporometry, and magnetic resonance imaging. The results show that weathering increased T2 relaxation time of lumens, indicating the degradation of tracheids and vessels, especially in TMW compared to unmodified wood. The amounts of bound water, FSP value, and cell wall pores were increased after weathering; however, an increase in thermal modification intensity resulted in lower FSP and limited the increase in number of pores. In summary, TMW showed better performance than unmodified wood after weathering.</jats:p

Effect of natural weathering on water absorption and pore size distribution in thermally modified wood determined by nuclear magnetic resonance

Funder: Teollisuusneuvos Heikki Väänänen's FundFunder: International Thermowood AssociationFunder: Quantum Institute, University of OuluAbstractThermally modified wood (TMW) is widely used in outdoor applications due to its advanced properties towards weathering stresses. Although the structure changes of TMW from weather factors have been reported, investigation of the quantitative analysis of water states and cell wall structure of TMW after weathering is limited. In this work, the amount of bound water, fiber saturation point (FSP), cell wall pores, and free water distribution of thermally modified Scots pine, Norway spruce, and European ash were measured before and after a 2-year natural weathering via NMR relaxometry, cryoporometry, and magnetic resonance imaging. The results show that weathering increased T2 relaxation time of lumens, indicating the degradation of tracheids and vessels, especially in TMW compared to unmodified wood. The amounts of bound water, FSP value, and cell wall pores were increased after weathering; however, an increase in thermal modification intensity resulted in lower FSP and limited the increase in number of pores. In summary, TMW showed better performance than unmodified wood after weathering.</jats:p

Spontaneous N-15 Nuclear Spin Hyperpolarization in Metal-Free Activation of Parahydrogen by Molecular Tweezers

The ability of frustrated Lewis pairs (FLPs) to activate H-2 is of significant interest for metal-free catalysis. The activation of H-2 is also the key element of parahydrogen-induced polarization (PHIP), one of the nuclear spin hyper polarization techniques. It is demonstrated that o-phenylene-based ansa-aminoboranes (AABs) can produce H-1 nuclear spin hyperpolarization through a reversible interaction with parahydrogen at ambient temperatures. Heteronuclei are useful in NMR and MRI as well because they have a broad chemical shift range and long relaxation times and may act as background-free labels. We report spontaneous formation of N-15 hyperpolarization of the N-H site for a family of AABs. The process is efficient at the high magnetic field of an NMR magnet (7 T), and it provides up to 350-fold N-15 signal enhancements. Different hyperpolarization effects are observed with various AAB structures and in a broad temperature range. Spontaneous hyperpolarization, albeit an order of magnitude weaker than that for N-15, was also observed for B-11 nuclei.Peer reviewe

Diffusion measurements of hydrocarbons in H-MCM-41 extrudates with pulsed-field gradient nuclear magnetic resonance spectroscopy

Mesoporous materials are promising catalysts for production of biofuels. Herein, H-MCM-41 catalysts with different concentrations of the silica Bindzil binder (10-50 wt%) were prepared and characterized using pulsed-field gradient (PFG) NMR in the powder form and as extrudates. Effective diffusion coefficients (D-e) are measured in all cases. Diffusivities of n-hexadecane were found smaller for extrudates as compared to the powder catalysts. The estimates of diffusive tortuosity were also determined. PFG NMR data showed one major component that reveals diffusion in interconnected meso- and micropores and one other minor component (1-2%) that may correspond to more isolated pores or may represent complex effects of restricted diffusion. Therefore, several approaches including initial slope analysis of spin-echo attenuation curves, two-component fitting and Laplace inversion were used to discuss different aspects of diffusional transport in the studied H-MCM-41 materials. Correlations between D-e and the amount of Bindzil, the specific surface area, the micropore volume, the particle size, the total acid sites and the Lewis acid sites are discussed