Aminopyridinato Complexes as Possible Alternatives for Metallocenes in Ethylene Polymerization

Polyethylene is the most widely used synthetic polymer in the world. Most polyethylene is made with Ziegler-Natta catalysts. Polyethylenes for special applications are made with metallocenes, which are nowadays heavily patented. It is laborious therefore, to develop new metallocenes. The aim of this work was to investigate the feasibility of replacing the cyclopentadienyl ligands of metallocenes by aminopyridinato ligands without losing the good properties of the metallocenes, such as high activity and formation of linear polymer. The subject was approached by studying what kind of catalysts the metallocenes are and how they catalyze polyethylene. The polymerization behavior of metallocenes was examined by synthesizing a piperazino substituted indenyl zirconocene catalyst and comparing its polymerization data with that of the indenyl zirconocene catalyst. On the basis of their isolobality, it was thought that aminopyridinato ligands might replace cyclopentadienyl ligands. It was presumed that the polymerization mechanism and the active center in ethylene polymerization would be similar for aminopyridinato and metallocene catalysts. Titanium aminopyridinato complexes were prepared and their structures determined to clarify the relationship between structure of the catalyst precursor and polymerization results. The ethylene polymerization results for titanium 2-phenylaminopyridinato catalysts and titanocene catalysts were compared.

Structure, function and intracellular dynamics of alphavirus replication complexes

Intracellular membrane alterations are hallmarks of positive-sense RNA (+RNA) virus replication. Strong evidence indicates that within these exotic compartments, viral replicase proteins engage in RNA genome replication and transcription. To date, fundamental questions such as the origin of altered membranes, mechanisms of membrane deformation and topological distribution and function of viral components, are still waiting for comprehensive answers. This study addressed some of the above mentioned questions for the membrane alterations induced during Semliki Forest virus (SFV) infection of mammalian cells. With the aid of electron and fluorescence microscopy coupled with radioactive labelling and immuno-cytochemistry techniques, our group and others showed that few hours after infection the four non structural proteins (nsP1-4) and newly synthesized RNAs of SFV colocalized in close proximity of small membrane invaginations, designated as spherules . These 50-70 nm structures were mainly detected in the perinuclear area, at the limiting membrane of modified endosomes and lysosomes, named CPV-I (cytopathic vacuoles type I). More rarely, spherules were also found at the plasma membrane (PM). In the first part of this study I present the first three-dimensional reconstruction of the CPV-I and the spherules, obtained by electron tomography after chemical or cryo-fixation. Different approaches for imaging these macromolecular assemblies to obtain better structure preservation and higher resolution are presented as unpublished data. This study provides insights into spherule organization and distribution of viral components. The results of this and other experiments presented in this thesis will challenge currently accepted models for virus replication complex formation and function. In a revisitation of our previous models, the second part of this work provides the first complete description of the biogenesis of the CPV-I. The results demonstrate that these virus-induced vacuoles, where hundreds of spherules accumulate at late stages during infection, represent the final phase of a journey initiated at the PM, which apparently serves as a platform for spherule formation. From the PM spherules were internalized by an endocytic event that required the activity of the class I PI3K, caveolin-1, cellular cholesterol and functional actin-myosin network. The resulting neutral endocytic carrier vesicle delivered the spherules to the membrane of pre-existing acidic endosomes via multiple fusion events. Microtubule based transport supported the vectorial transfer of these intermediates to the pericentriolar area where further fusions generated the CPV-I. A signal for spherule internalization was identified in one of the replicase proteins, nsP3. Infections of cells with viruses harbouring a deletion in a highly phosphorylated region of nsP3 did not result in the formation of CPV-Is. Instead, thousands of spherules remained at the PM throughout the infection cycle. Finally, the role of the replicase protein nsP2 during viral RNA replication and transcription was investigated. Three enzymatic activities, protease, NTPase and RNA-triphosphatase were studied with the aid of temperature sensitive mutants in vitro and, when possible, in vivo. The results highlighted the interplay of the different nsP2 functions during different steps of RNA replication and sub-genomic promoter regulation, and suggest that the protein could have different activities when participating in the replication complex or as a free enzyme.

Diffusion of Be, Co and Mn impurities in compound semiconductors and glassy carbon studied by the modified radiotracer technique

The main method of modifying properties of semiconductors is to introduce small amount of impurities inside the material. This is used to control magnetic and optical properties of materials and to realize p- and n-type semiconductors out of intrinsic material in order to manufacture fundamental components such as diodes. As diffusion can be described as random mixing of material due to thermal movement of atoms, it is essential to know the diffusion behavior of the impurities in order to manufacture working components. In modified radiotracer technique diffusion is studied using radioactive isotopes of elements as tracers. The technique is called modified as atoms are deployed inside the material by ion beam implantation. With ion implantation, a distinct distribution of impurities can be deployed inside the sample surface with good con- trol over the amount of implanted atoms. As electromagnetic radiation and other nuclear decay products emitted by radioactive materials can be easily detected, only very low amount of impurities can be used. This makes it possible to study diffusion in pure materials without essentially modifying the initial properties by doping. In this thesis a modified radiotracer technique is used to study the diffusion of beryllium in GaN, ZnO, SiGe and glassy carbon. GaN, ZnO and SiGe are of great interest to the semiconductor industry and beryllium as a small and possibly rapid dopant hasn t been studied previously using the technique. Glassy carbon has been added to demonstrate the feasibility of the technique. In addition, the diffusion of magnetic impurities, Mn and Co, has been studied in GaAs and ZnO (respectively) with spintronic applications in mind.

Representation av kvinnor och män – Hur prioriterar riksdagsledamöter frågor i den finska riksdagen? En kvantitativ studie av motionerna i riksdagen 2007

Pro gradu uppsatsen diskuterar betydelsen av representation för grupper i samhället genom att diskutera kvinnors representation. Kvinnor är en grupp i samhället som länge varit underrepresenterad, men som under de senaste 100 åren fått en betydligt bättre position i den offentliga beslutfattningen. För att ge bakgrund till frågeställningen beskrivs kvinnors deltagande i den finska riksdagen. Begreppen deskriptiv, substantiell och symbolisk representation diskuteras. Undersökningar av kvinnors representation både deskriptivt och substantiellt på parlamentsnivå presenteras. Forskningsfrågan i uppsatsen består av fyra frågeställningar om hur motioner görs i riksdagen och hur kön kan identifieras i motionerna. Frågeställningarna bygger på den teoretiska diskussionen och meningen med frågeställningar är att styra analysen av motionerna. I teoriavsnittet behandlas kvinnors representation och den vetenskapliga diskussionen om sambandet mellan substantiell och deskriptiv representation. Diskussionen utgår från Hanna Pitkins olika kategorier av representation. I den teoretiska diskussionen behandlas även begreppen den kritiska massan, närvarons politik och kritiska aktörer. I stycket diskuteras även vilka frågeställningar, som är relevanta att undersöka när man diskuterar kvinnors representation i samhället. När representationen av kvinnor diskuteras är det viktigt att minnas att kvinnor inte utgör en homogen grupp och att även män kan representera kvinnor innehållsmässigt. Efter den teoretiska diskussionen presenteras metoden för undersökningen. Som metod används kvantitativa statistiska metoder för att kunna undersöka ett större material, som kan ge en bättre helhetsbild av hur kvinnor representeras i motionerna. Materialet för undersökningen är motioner som är gjorda i den finska riksdagen 2007. Resultaten i undersökningen visar att motionerna används av både opposition och regering och att det finns en möjlighet för samarbete över partigränser. Andra faktorer, som påverkade hur aktivt man gjorde motioner var bland annat riksdagsledamöternas ålder och den valregion ledamöterna var från. När man såg speciellt på motionärernas kön framkom det skillnader i kvinnors och mäns motionsbeteende. Överlag gör män mera motioner än kvinnor i den finska riksdagen. Kvinnor har än idag en större tendens att göra motioner om socialpolitik och speciellt familje- och barnpolitik än vad män har. Männen igen väljer att göra motioner, som traditionellt har setts som starkt manliga, så som trafik och allmänna utrymmen. Resultaten visade också att kvinnors intressen inte är vanligt som motivering för motioner. Man fann också att riksdagsledamöters koppling till kvinnoorganisationer hade en betydelse när det gällde sannolikheten att göra motioner som motiverades med kvinnors intressen i samhället. Uppsatsen diskuterar orsaker till resultaten och ser att det finns orsaker att fortsätta diskutera sambandet mellan deskriptiv och substantiell representation.