Synthesis, Structure, Spirocyclization Mechanism, and Glutathione Peroxidase-like Antioxidant Activity of Stable Spirodiazaselenurane and Spirodiazatellurane

The first examples of stable spirodiazaselenurane and spirodiazatellurane were synthesized by oxidative spirocyclization of the corresponding diaryl selenide and telluride and were structurally characterized. X-ray crystal structures of the spirodiazaselenurane and spirodiazatellurane suggest that the structures are distorted trigonal bipyramidal (TBP) with the electronegative nitrogen atoms occupying the apical positions and two carbon atoms and the lone pair of Se/Te occupying the equatorial positions. Interestingly, the spirodiazatellurane underwent spontaneous chiral resolution during crystallization, and the absolute configurations of its enantiomers were confirmed by single-crystal X-ray analyses. A detailed mechanistic study indicates that the cyclization to spirodiazaselenurane and spirodiazatellurane occurs via selenoxide and telluroxide intermediates. The chalcogenoxides cyclize to the corresponding spiro compounds in a stepwise manner via the involvement of hydroxyl chalcogenurane intermediates, and the activation energy for them spirocyclization reaction decreases in the order S > Se > Te. In addition to the synthesis, characterization, and mechanism of cyclization, the glutathione peroxidase (GPx) mimetic activity of the newly synthesized compounds was evaluated. These studies suggest that the tellurium compounds are more effective as GPx mimics than their selenium counterparts due to the fast oxidation of the tellurium center in the presence of peroxide and the involvement of an efficient redox cycle between the telluride and telluroxide intermediate.

Inhibitory activity of Image -asparaginase from Mycobcacterium tuberculosis on Yoshida ascites sarcoma in rats

The antitumor activity of Image -asparagine amidohydrolases (EC 3.5.1.1) from Mycobacterium tuberculosis H37Rv and H37Ra strains has been tested on Yoshida ascites sarcoma in rats. The enzyme specific to M. tuberculosis H37Ra but not to H37Rv has proved to be effective in inhibiting the growth of the sarcoma. Comparative studies on the activity of this enzyme with that of similar enzyme from Escherichia coli B, has shown that at the same levels the former is more effective than the latter. Long-lived immunity to this tumor in A/IISc Wistar rats following treatment of tumor bearing animals with M. tuberculosis H37Ra, pH 9.6 Image -asparaginase has been observed. Immunity in these rats was demonstrated by tumor rejection and detection of humoral antibodies in the sera to the antigen of the cell-free extract of the tumor. The enzyme was ineffective in inhibiting fibrosarcoma in mice at the dose levels tested.

Physical activity and diabetic complications in patients with type 1 diabetes

Type 1 diabetes is associated with the risk for late diabetic complications which are divided into microvascular (retinopathy, nephropathy, and neuropathy) and macrovascular (cardiovascular disease, CVD) diseases. The risk for diabetic complication can be reduced by effective treatment, most importantly the glycaemic control. Glycaemia in type 1 diabetes is influenced by the interplay between insulin injections and lifestyle factors such as physical activity and diet. The effect of physical activity in patients with type 1 diabetes is not well known, however. The aim of this thesis was to investigate the physical activity and the physical fitness of patients with type 1 diabetes with special emphasis on glycaemic control and the diabetic complications. The patients included in the study were all part of the nationwide, multicenter Finnish Diabetic Nephropathy (FinnDiane) Study which aims to characterise genetic, clinical, and environmental factors that predispose to diabetic complications in patients with type 1 diabetes. In addition, subjects from the IDentification of EArly mechanisms in the pathogenesis of diabetic Late complications (IDEAL) Study were studied. Physical activity was assessed in the FinnDiane Study in 1945 patients by a validated questionnaire. Physical fitness was measured in the IDEAL Study by spiroergometry (cycle test with measurement of respiratory gases) in 86 young adults with type 1 diabetes and in 27 healthy controls. All patients underwent thorough clinical characterisation of their diabetic complication status. Four substudies were cross-sectional using baseline data and one study additionally used follow-up data. Physical activity, especially the intensity of activities, was reduced in patients affected by diabetic nephropathy, retinopathy, and CVD. Low physical activity was associated with poor glycaemic control, a finding most clear in women and evident also in patients with no signs of diabetic complications. Furthermore, low physical activity was associated with a higher HbA1c variability, which in turn was associated with the progression of renal disease and CVD during follow-up. A higher level of physical activity was also associated with better insulin sensitivity. The prevalence of the metabolic syndrome in type 1 diabetes was also lower the higher the physical activity. The aerobic physical fitness level of young adults with type 1 diabetes was reduced compared with healthy peers and in men an association between higher fitness level and lower HbA1c was observed. In patients with type 1 diabetes, a higher physical activity was associated with better glycaemic control and may thus be beneficial with respect to the prevention of diabetic complications.

Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative order. 3, 6 (dppz)> 2, 5 (dpq) > 1, 4 (phen) The binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Alppihiihdon alkutaival : Pujottelu- ja tunturihiihto Suomessa 1920-luvulta 1960-luvulle

The object of study in this thesis is Finnish skiing culture and Alpine skiing in particular from the point of view of ethnology. The objective is to clarify how, when, why and by what routes Alpine skiing found its way to Finland. What other phenomena did it bring forth? The objective is essentially linked to the diffusion of modern sports culture to Finland. The introduction of Alpine skiing to Finland took place at a time when skiing culture was changing: flat terrain skiing was abandoned in favour of cross-country skiing in the early decades of the 20th century, and new techniques and equipment made skiing a much more versatile sport. The time span of the study starts from the late 19th century and ends in the mid-20th century. The spatial focus is in Finland. People and communities formed through their actions are core elements in the study of sports and physical activity. Organizations tend to raise themselves into influential actors in the field of physical culture even if active individuals work in their background. Original archive documents and publications of sports organizations are central source material for this thesis, complemented by newspapers and sports magazines as well as photographs and films on early Alpine skiing in Finland. Ever since their beginning in the late 19th century skiing races in Finland had mostly taken place on flat terrain or sea ice. Skiing in broken cross-country terrain made its breakthrough in the 1920 s, at a time when modern skiing techniques were introduced in instruction manuals. In the late 1920 s the Finnish Women s Physical Education Association (SNLL) developed unconventional forms of pedagogical skiing instruction. They abandoned traditional Finnish flat terrain skiing and boldly looked for influences abroad, which caused friction between the leaders of the women s sports movement and the (male) leaders of the central skiing organization. SNLL was instrumental in launching winter tourism in Finnish Lapland in 1933. The Finnish Tourism Society, the State Railways and sports organizations worked in close co-operation to instigate a boom in tourism, which culminated in the inauguration of a tourist hotel at Pallastunturi hill in the winter of 1938. Following a Swedish model, fell-skiing was developed as a domestic counterpart to Alpine skiing as practiced in Central Europe. The first Finnish skiing resorts were built at sites of major cross-country skiing races. Inspired by the slope at Bad Grankulla health spa, the first slalom skiing races and fell-skiing, slalom enthusiasts began to look for purpose-built sites to practice turn technique. At first they would train in natural slopes but in the late 1930 s new slopes were cleared for slalom races and recreational skiing. The building of slopes and ski lifts and the emergence of organized slalom racing competitions gradually separated Alpine skiing from the old fell-skiing. After the Second World War fell-skiing was transformed into ski trekking on marked courses. At the same time Alpine skiing also parted ways with cross-country skiing to become a sport of its own. In the 1940 s and 1950 s Finnish Alpine skiing was almost exclusively a competitive sport. The specificity of Alpine skiing was enhanced by rapid development of equipment: the new skis, bindings and shoes could only be used going downhill.

Studies on the enzyme hydrolysing flavin mononucleotide in plants: II. Phosphotransferase activity of the partially purified enzyme from Phaseolus radiatus

The preparation of the enzyme hydrolysing FMN whose partial purification from green-gram extracts is described in the preceding paper, has been shown to possess phosphotransferase activity. The enzyme could transfer the phosphate group cleaved from FMN to acceptors like thiamine, pyridoxal, pyridoxamine and nucleosides resulting in the formation of their corresponding phosphate esters and nucleotides. The properties of the enzyme hydrolysing FMN and the phosphotransferase activity of the preparation are compared.

Pt2+ Dispersed in Ce0.83Ti0.15O2-delta: Significant Improvement in PROX Activity by Ti Substitution in CeO2 in Hydrogen Rich Stream

Pt2+ ion dispersed in CeO2, Ce1-xTixO2-delta and TiO2 have been tested for preferential oxidation of carbon monoxide (PROX) in hydrogen rich stream. It is found that Pt2+ substituted CeO2 and Ce(1-x)TixO(2-delta) in the form of solid solution Ce0.98Pt0.02O2-delta and Ce0.83Ti0.15Pt0.02O2-delta are highly CO selective low temperature PROX catalysts in hydrogen rich stream. Just 15% of Ti substitution in CeO2 improves the overall PROX activity.

The Relationship Between Liquidity, Trading Activity and Return - Studies of the Finnish and Swedish Stock Markets

Liquidity, or how easy an investment is to buy or sell, is becoming increasingly important for financial market participants. The objective of this dissertation is to contribute to the understanding of how liquidity affects financial markets. The first essays analyze the actions taken by underwriters immediately after listing to improve liquidity of IPO stock. To estimate the impact of underwriter activity on the pricing of the IPOs, the order book during the first weeks of trading in the IPO stock is studied. Evidence of stabilization and liquidity enhancing activities by underwriters is found. The second half of the dissertation is concerned with the daily trading of stocks where liquidity may be impacted by policy issues such as changes in taxes or exchange fees and by opening the access to the markets for foreign investors. The desirability of a transaction tax on securities trading is addressed. An increase in transaction tax is found to cause lower prices and higher volatility. In the last essay the objective is to determine if the liquidity of a security has an impact on the return investors require. The results support the notion that returns are negatively correlated to liquidity.

Photocatalytic activity of tin-substituted TiO2 in visible light

Ultrafine powders of (Ti1-xSnx)O2, 0activity (after platinization) in the visible light region (420-550 nm) for H2 production from aqueous solutions containing sacrificial donors such as hypophosphite. The spectral sensitization is shown to be due to peroxotitanium species present in the lattice.