Synthesis, Structure, and Solid-State Transformation Studies of Phosphonoacetate Based Hybrid Compounds of Uranium and Thorium

Three new phosphonoacetate hybrid frameworks based on the actinide elements uranium and thorium have been synthesized. The compounds [C4N2H14][(UO2)(2)(O3PCH2COO)(2)]center dot H2O, I,[C4N2H14][(UO2)(2)(C2O4)(O3PCH2COOH)(2)], II, and Th(H2O)(2)(O3PCH2COO)(C2O4)(0.5). H2O, III, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units. Compound II has been prepared using a solvent-free approach, by a solid state reaction at 150 degrees C. It has been shown that II can also be prepared through a room temperature mechanochemical (grinding) route. The layer arrangement in III closely resembles to that observed in I. The compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and fluorescence studies.

“Empire is a state of mind” – Imagining Eurasia in Russia –

Työssäni tarkastelen venäläistä neo-euraasianistista liikettä ja tapoja joilla liikkeen aktivistit rakentavat Euraasiasta yhtenäistä kokonaisuutta ja imperiumia. Keskeisiä tutkimuskysymyksiäni ovat: Mikä imperiumi on ja mitkä ovat sen keskeisiä motivaatioita ja teemoja? Kuinka imperiumin idea rakentuu tai käsitetään ja tämän voi tulkita? Minkälaisia seurauksia voi tulkita heidän tavallaan Euraasia nähdä olevan? Materiaalina käytän haastatteluja, jotka on kerätty Moskovassa keväällä 2008, ja liikkeen kirjallisia tuotoksia (lehdet ja Internet -sivut). Neo-euraasianistisella liikkeellä tarkoitan tässä työssä Kansainvälistä Euraasianistista liikettä (Meždunarodnoe Evrazijskoe Dviženie) ja sen alahaaraa Euraasianistista Nuorisoliittoa (Evrazijskij Sojuz Molodëži). Liike perustettiin virallisesti 2003, mutta rakentaa vahvasti historiallista yhteyttä 1930 -luvun klassiseen eurasianismiin. Tämän lisäksi sen diskurssissa on paljon neuvostoliittolaisia, fasistisia, uuskonservatiivisia ja nationalistisia piirteitä. Liikkeen johtohahmo on filosofi-geopoliitikko Alexandr Dugin. Työn tausta-ajatuksena minua kiinnostaa etenkin nk. älymystön tai intelligenttien vaikutus nationalismiin tai sosiaalisia ryhmiä määrittelevien diskurssien kehitykseen ja muutokseen.Tarkastelen materiaalia diskurssianalyyttisesta näkökulmasta. Näen diskurssianalyysin sen tutkimisena, miten sosiaalista todellisuutta tuotetaan erilaisissa sosiaalisissa käytännöissä. Samalla näiden diskurssien tutkiminen, foucautlaisen perinteen myötä, tarkastelee kriittisesti niiden tuottamia (aktualisoituneita sekä potentiaalisia) valtasuhteita. Käytän työssäni myös Benedict Andersonin kuvitellun yhteisön (imagined communities) käsitettä, joka auttaa hahmottamaan tapaa, jolla tutkimuskohteeni rakentavat imperiumia yhteisönä. Aktivistien puheessa imperiumi (imperiâ) tulee esiin pääasiallisesti positiivisesti ja ”heidän omanaan,” kun taas termi imperialismi (imperializm) pääosin negatiivisena, liittyen etenkin keskeisenä vihollisena pidettyihin Yhdysvaltoihin. Esiin nousee monta toisiinsa liittyvää teemaa, jotka jaottelen viideksi pääteemaksi. Näistä tarkastelen lähemmin imperiumia ”kaikkien kansojen hyväntekijänä (poliittinen puoli)”, ulkoisen voiman lähteenä (historiallis-geopoliittinen puoli) sekä kollektiivisen subjektin luojana (imperialistis-nationalistinen puoli). Pyrin kontekstualisoimaan diskurssin ja tarkastelemaan tapoja, joilla se ammentaa motiiveja myös historiallis-kulttuurisista tavoista hahmottaa aluetta ja sen asukkaita. Käsittelen myös kansan, kansakunnan, etnoksen ja nationalismin käsitteitä ja sitä, miten ne nousevat neo-eurasianistisessa diskursissa esiin. Imperiaalisen nationalismin (imperskij nacionalizm) käsite auttaa ymmärtämään niitä tapoja, jolla liike tekee sekä pesäeroa nationalismiin että samalla hyödyntää monia nationalistisen diskurssin perusteemoja. Eräs liikkeen diskurssin keskeisistä eroista niin sanottuun nationalismin valtavirtaan on ”kansakunnan (naciâ)” käsitteen vahva negatiivinen konnotaatio. Sen vastakohtana esiin nostetaan vahvasti kansan (narod) käsite. Samalla kuitenkin etnisen venäläisen (russkij) käsitettä käytetään tavallista laajemmin ja kattavammin kuin tavallisesti, ja ennen kaikkea Venäjä nousee imperiumin keskeisimmäksi tekijäksi. Euraasialaiseen imperiumiin liitetyistä positiivistista mielikuvista käsittelen tarkemmin monikansallisuuden ja kansojen kodin ideaa, joka nousee mielestäni huomattavaksi retoriseksi taustaksi kaikessa materiaalissa. Tähän liittyy vahvasti myös saman teeman sivujuonne, eli imperiumin ”vapauttava” rooli. Tulkitsen, että liikkeen imperiumi -diskurssilla on instrumentaalinen luonne: se legitimoi aktivistien vaatimuksia varsinkin entisen Neuvostoliiton alueen suhteen. ”Euraasialaisen kansan” ajatus toimii mahdollisena Euraasiaa yhteisenä tekijänä ”Neuvostokansan” tilalla. Sen taustalla materiaalistani päätellen siintävät kuitenkin enemmänkin Venäjä ja venäläis -spesifit vaateet kuin koko Euraasia. Pohdin myös kansakunnan (nation) hyljeksimisen syitä ja käsitteen sopivuutta Venäjälle, kuten myös venäläisyyden käsitteiden kerrostuneisuutta. Kokonaisuudessaan imperiumi tuli esiin abstraktina, utopistisena ja ”totaalisena” kokonaisuutena.

On The Ground State Properties Of The +/-J Ising Model

In the combinatorial method or Grassmann algebra formalism the ground state properties of the f J Ising model can be expressed in terms of the behaviour of the eigenvectors of a matrix. It is shown that a transition from localized to extended eigenvectors signals the breakdown of ferromagnetic rigidity.

Vitamin A and thyroxine carrier proteins in chicken plasma Steady-state control of the plasma level of free retinol-binding protein and free thyroxine

1. 1. The binding parameters of prealbumin-2 with retinol-binding protein and thyroxine (T4) revealed the existence of distinct and multiple sites for both retinol-binding protein and T4. 2. 2. From the analysis of binding parameters of retinol-binding protein with prealbumin-2 it is clear that under steady-state conditions about 99% of the holo-retinol-binding protein remains bound to prealbumin-2. 3. 3. Equilibrium dialysis studies on binding properties of thyroid hormones with prealbumin-2 revealed that it has a single high affinity site and three low affinity sites. 4. 4. The occurrence of three carrier proteins for thyroid hormones, thyroxine-binding globulin, prealbumin-2 and albumin has been demonstrated. However, the chicken thyroxine-binding globulin differs from human thyroxine-binding globulin by being relatively less acidic and occuring at a two-fold lower concentration. But the thyroid hormone binding parameters are comparable. 5. 5. Highly sensitive methods were developed for determination of T4 binding capacities of the various proteins and plasma level of total T4 by fractionation of carrier proteins and further quantitatively employing in electrophoresis and equilibrium dialysis. 6. 6. The thyroxine-binding proteins were found to be two types, one (viz., thyroxine-binding globulin) of great affinity but of low binding capacity, which mainly acts as reservoir of T4, and another (viz.,prealbumin-2) of low affinity but of high binding capacity, which can participate predominantly in the control of the free T4 pool.

First-principles analysis of electron correlation, spin ordering and phonons in the normal state of FeSe1-x

We present first-principles density-functional-theory-based calculations to determine the effects of the strength of on-site electron correlation, magnetic ordering, pressure and Se vacancies on phonon frequencies and electronic structure of FeSe1-x. The theoretical equilibrium structure (lattice parameters) of FeSe depends sensitively on the value of the Hubbard parameter U of on-site correlation and magnetic ordering. Our results suggest that there is a competition between different antiferromagnetic states due to comparable magnetic exchange couplings between first- and second-neighbor Fe sites. As a result, a short range order of stripe antiferromagnetic type is shown to be relevant to the normal state of FeSe at low temperature. We show that there is a strong spin-phonon coupling in FeSe (comparable to its superconducting transition temperature) as reflected in large changes in the frequencies of certain phonons with different magnetic ordering, which is used to explain the observed hardening of a Raman-active phonon at temperatures (similar to 100 K) where magnetic ordering sets in. The symmetry of the stripe antiferromagnetic phase permits an induced stress with orthorhombic symmetry, leading to orthorhombic strain as a secondary order parameter at the temperature of magnetic ordering. The presence of Se vacancies in FeSe gives rise to a large peak in the density of states near the Fermi energy, which could enhance the superconducting transition temperature within the BCS-like picture.

On the charging state of atmospheric aerosols and ion-induced nucleation

Floating in the air that surrounds us is a number of small particles, invisible to the human eye. The mixture of air and particles, liquid or solid, is called an aerosol. Aerosols have significant effects on air quality, visibility and health, and on the Earth's climate. Their effect on the Earth's climate is the least understood of climatically relevant effects. They can scatter the incoming radiation from the Sun, or they can act as seeds onto which cloud droplets are formed. Aerosol particles are created directly, by human activity or natural reasons such as breaking ocean waves or sandstorms. They can also be created indirectly as vapors or very small particles are emitted into the atmosphere and they combine to form small particles that later grow to reach climatically or health relevant sizes. The mechanisms through which those particles are formed is still under scientific discussion, even though this knowledge is crucial to make air quality or climate predictions, or to understand how aerosols will influence and will be influenced by the climate's feedback loops. One of the proposed mechanisms responsible for new particle formation is ion-induced nucleation. This mechanism is based on the idea that newly formed particles were ultimately formed around an electric charge. The amount of available charges in the atmosphere varies depending on radon concentrations in the soil and in the air, as well as incoming ionizing radiation from outer space. In this thesis, ion-induced nucleation is investigated through long-term measurements in two different environments: in the background site of Hyytiälä and in the urban site that is Helsinki. The main conclusion of this thesis is that ion-induced nucleation generally plays a minor role in new particle formation. The fraction of particles formed varies from day to day and from place to place. The relative importance of ion-induced nucleation, i.e. the fraction of particles formed through ion-induced nucleation, is bigger in cleaner areas where the absolute number of particles formed is smaller. Moreover, ion-induced nucleation contributes to a bigger fraction of particles on warmer days, when the sulfuric acid and water vapor saturation ratios are lower. This analysis will help to understand the feedbacks associated with climate change.

Simplified Analysis of Steady-State Performance of a Voltage Controlled Induction Motor Drive

Utilizing a circuit model [1, 2] of an induction motor, a simplified analysis of steady state performance of a voltage controlled induction motor (VCIM) drive is described in this paper. By solving a set of nonlinear algebraic equations which describe the VCIM drive under steady operation, the operating variables such as constant components of torque, rotor flux linkages, fundamental components of stator voltage and current and phase angle are obtained for any given value of slip, triggering angle and supply voltage.

Solid-state chemistry of high-temperature oxide superconductors:The experimental situation

High-temperature superconductivity in oxides of the type(La, Ln)2?xBax(Sr)xCuO4, Y(Ln)Ba2Cu3O7??, La3?xBa3+xCu6O14, and related systems is discussed with emphasis on aspects related to experimental solid-state chemistry. All of these oxides possess perovskite-related structures. Oxygen-excess and La-deficient La2CuO4 also exhibit superconductivity in the 20�40 K just as La2?xBax(Srx)CuO4; these oxides are orthorhombic in the superconductivity phase. The crucial role of oxygen stoichiometry in the superconductivity ofYBa2Cu3O7?? (Tc = 95 ± 5K) is examined; this oxide remains orthorhombic up to ? ? 0.6 and becomes tetragonal and nonsuperconducting beyond this value of ?. Oxygen stoichiometry in this and related oxides has to be understood in terms of structure and disorder. The structure of La3?xBa3+xCu6O14 is related to that of YBa2Cu3O7, the orthorhombic structure manifesting itself when the population of O1 oxygens (along the Cusingle bondOsingle bondCu chains) is preponderant compared to that of O5 oxygens (along thea-axis); nearly equal populations of O1 and O5 sites give rise to the tetragonal structure. A transition from a high-Tc (95 K) superconductivity regime to a low-Tc (not, vert, similar60 K) regime occurs in YBa2Cu3O7?? accompanying a change in ?. There is no evidence for Cu3+ in these nominally mixed valent copper oxides. Instead, holes are present on oxygens giving rise to O? or O2?2 species, the concentration of these species increasing with the lowering of temperature. Certain interesting aspects of the superconducting oxides such as domain or twin boundaries, Raman spectra, microwave absorption, and anomalous high-temperature resistivity drops are presented along with the important material parameters. Preparative aspects of the superconducting oxides are briefly discussed. Phase transitions seem to occur atTc as well as at not, vert, similar240 K in YBa2Cu3O7.

Steady-State Stability of Current Mode Active-Clamp ZVS DC-DC Converters

Active-clamp dc-dc converters are pulsewidth-modulated converters having two switches featuring zero-voltage switching at frequencies beyond 100 kHz. Generalized equivalent circuits valid for steady-state and dynamic performance have been proposed for the family of active-clamp converters. The active-clamp converter is analyzed for its dynamic behavior under current control in this paper. The steady-state stability analysis is presented. On account of the lossless damping inherent in the active-clamp converters, it appears that the stability region in the current-controlled active-clamp converters get extended for duty ratios, a little greater than 0.5, unlike in conventional hard-switched converters. The conventional graphical approach fails to assess the stability of current-controlled active-clamp converters due to the coupling between the filter inductor current and resonant inductor current. An analysis that takes into account the presence of the resonant elements is presented to establish the condition for stability. This method correctly predicts the stability of the current-controlled active-clamp converters. A simple expression for the maximum duty cycle for subharmonic free operation is obtained. The results are verified experimentally.

Structure of 6-acetoxycoumarin: topochemical photodimerization and analysis of acetoxy...acetoxy interactions in the solid state

C~HaO 4, Mr=204.2, monoclinic, P2Jn,a=3.900(1), =37.530(6), c=6.460(1)A, fl=103.7 (1) °, V= 918.5 (5) A 3, Z = 4, D m = 1.443, D x --- 1.476 Mg m -3, Cu Ks, 2 = 1.5418 ,/k, /t = 0.86 mm -~, F(000) = 424, T= 293 K, R = 0.075 for 1019 significant reflections. Molecules pack in fl-type stacking mode which is characterized by the close packing of parallel and nearly planar reactive double bonds with a separation of 3.900/~ along the a axis.The syn head-head dimer obtained is the direct consequence of this packing arrangement. Molecular packing is stabilized by intermolecular C-H...O hydrogen bonding. Analysis of acetoxy...acetoxy interactions in the acetoxy compounds retrieved from the Cambridge Structural Database reveal that the majority of them are anti-dipolar.

Use of the Nasicon/Na2SO4 couple in a solid state sensor for SOx (x=2,3)

The e.m.f. of a concentration cell for SO x (x=2,3)-O2 incorporating Nasicon as the main solid electrolyte has been measured in the temperature range 720 to 1080 K. The cell arrangement can be represented as,$$Pt, O'_2 + SO'_2 + SO'_3 \left| {Na_2 SO_4 \left\| {\left. {Nasicon} \right\|} \right.} \right.\left. {Na_2 SO_4 } \right|SO''_3 + SO''_2 + O''_2 , Pt$$ The Na2SO4 acts both as an auxiliary electrode, converting chemical potentials of SO x and O2 to equivalent sodium potentials, and as an electrolyte. The presence of Na2SO4 provides partial protection of Nasicon from chemical reaction with gas mixtures containing SO x . The open circuit e.m.f. of the cell is in close agreement with values given by the Nernst equation. For certain fixed inlet gas compositions of SO2+O2, the e.m.f. varies non-linearly with temperature. The intrinsic response time of the cell to step changes in gas composition is estimated to vary from sim2.0 ksec at 723K to sim 0.2 ksec at 1077K. The cell functions well for large differences in partial pressures of SO3(pPrimeSO 3/pprimeSO 3ap104) at the electrodes.

Kalman Filter Algorithm for Rating and Prediction in Basketball

The Thesis presents a state-space model for a basketball league and a Kalman filter algorithm for the estimation of the state of the league. In the state-space model, each of the basketball teams is associated with a rating that represents its strength compared to the other teams. The ratings are assumed to evolve in time following a stochastic process with independent Gaussian increments. The estimation of the team ratings is based on the observed game scores that are assumed to depend linearly on the true strengths of the teams and independent Gaussian noise. The team ratings are estimated using a recursive Kalman filter algorithm that produces least squares optimal estimates for the team strengths and predictions for the scores of the future games. Additionally, if the Gaussianity assumption holds, the predictions given by the Kalman filter maximize the likelihood of the observed scores. The team ratings allow probabilistic inference about the ranking of the teams and their relative strengths as well as about the teams’ winning probabilities in future games. The predictions about the winners of the games are correct 65-70% of the time. The team ratings explain 16% of the random variation observed in the game scores. Furthermore, the winning probabilities given by the model are concurrent with the observed scores. The state-space model includes four independent parameters that involve the variances of noise terms and the home court advantage observed in the scores. The Thesis presents the estimation of these parameters using the maximum likelihood method as well as using other techniques. The Thesis also gives various example analyses related to the American professional basketball league, i.e., National Basketball Association (NBA), and regular seasons played in year 2005 through 2010. Additionally, the season 2009-2010 is discussed in full detail, including the playoffs.