A Unique Nickel System having Versatile Catalytic Activity of Biological Significance

A new dinuclear nickel(II) complex, [Ni-2(LH2)(H2O)(2)(OH)(NO3)](NO3)(3) (1), of an "end-off" compartmental ligand 2,6-bis(N-ethylpiperazine-iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.

Conformationally restricted formyl methionyl tripeptide chemoattractants: a three-dimensional structure-activity study of analogs incorporating a C alpha,alpha-dialkylated glycine at position 2

The conformationally restricted CHO-L-Met-Xxx-L-Phe-OY (where Xxx = Aib, Ac3c, Ac5c, Ac6c, and Ac7c; Y = H, Me) tripeptides, analogs of the chemoattractant CHO-L-Met-L-Leu-L-Phe-OH, have been synthesized in solution by classical methods and fully characterized. Compounds were compared to determine the combined effect of backbone conformational preferences and side-chain bulkiness on the relation of three-dimensional structure to biological activity. Each peptide was tested for its ability to induce granule enzyme secretion from rabbit peritoneal polymorphonuclear leukocytes. In parallel, a conformational analysis on the CHO-blocked peptide and their tertbutyloxycarbonylated synthetic precursors was performed in the crystal state and in solution using X-ray diffraction, infrared absorption, and 1H nuclear magnetic resonance. The biological and conformational data are discussed in relation to the proposed model of the chemotactic peptide receptor of rabbit neutrophils.

Growing Flowers in the Frost: Civic Activity, Citizenship and Gender in Russia

This study analyzes civic activity, citizenship and their gendered manifestations in contemporary Russia. It is based on a case study conducted in the city of Tver , located in the vicinity of Moscow, during 2001-2005. The data consists of interviews with civic activists and municipal and regional authorities; observations of civic organizations; and a quantitative survey conducted among local civic groups. The theoretical and methodological framework of the study draws upon a micro perspective on organization, discourse analysis, gender and citizenship theories and Pierre Bourdieu s theory of fields and capital. This study develops theoretical understanding of the characteristics and logic of civic organization in Russia. It shows that social class centrally structures the field of civic activity. Organizations can be seen as a vehicle of the educated class to advocate their interests, help themselves and seek both social and individual-level change. The study also argues that civic organizations founded during the post-Soviet era are often an institutionalized form of informal social networks. Networks, which were a central element of everyday interaction in Soviet society, are a resource and often the only resource available that can be made use of in contemporary organizational activities. The study argues that gender operates as a key structuring principle in the Russian socio-political community. Civic activity is often discursively associated with femininity and institutional politics with masculinity. Women tend to participate more than men in civic organizations, while men dominate the formal political domain. The study shows that civic organizations are important loci of communality. This communality, however, differs from the communality envisioned in the communitarian and social capital debates in the West. It is selective communality , as it is restricted to the members of the organizations and does not create generalized reciprocity and trust. Civic organizations tend to build upon and reproduce the traditional Russian organizational form of circles , kruzhki. Along with the analysis of civic activities, the study also examines the redefinition of the role and functions of the state. The authorities interviewed in this study understand civic organizations as serving those goals and interests determined by the authorities, instead of viewing them as sites of citizens self-organization around interests and problems citizens themselves deem important, or as a counterforce to the state. By contrast, civic activists understand the core of organizational activity to be advocacy of their interests and rights, tackling social problems, the pursuit of wider social change and self-help. Co-operation between authorities and organizations tends to be personified and based upon unequal, hierarchical patron-client arrangements, which inhibits the development of democratic governance. The study will be published in Routledge Contemporary Russia and Eastern Europe Series later this year.

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.

Constructing Fair Tourism in Ecuador: The Case of Asoguabo

Tämän pro gradu-tutkielman tarkoitus on tutkia, miten reilun kaupan banaania tuottavan El Guabon pienten banaaninviljelijöiden järjestön Asoguabon reilun turismin projekti on rakennettu. Projektin muotoutumista tutkitaan tässä työssä kahdesta eri näkökulmasta: siitä, miksi ja miten Asoguabo on monipuolistanut viljelystä turismiin, sekä siitä, millainen kuva projektista on rakennettu markkinoinnin kautta ja miten reilun kaupan mainonnasta tuttuja ilmiöitä on hyödynnetty reilun turismin rakentamisessa. Tutkielman teoreettisena taustana on maaseudun muutoksia tarkasteleva uuden ruraliteetin käsite. Turismi on viime vuosikymmenten aikana muuttunut, ja matkailijat etsivät yhä enemmän aitoja ja autenttisia matkailukokemuksia. Samanaikaisesti turismia on tuotteistettu korostamalla sen tiettyjä, kestävän kehityksen mukaisia piirteitä, ja erityisesti kehittyvissä maissa turismia markkinoidaan usein vaihtoehtoisena, yhteisöpohjaisena tai ekoturismina. Reilu turismi on uutena käsitteenä tullut mukaan tähän laajaan kirjoon, ja tämä tutkielma käsitteleekin Asoguabon projektia nimenomaan reilun turismin näkökulmasta. Tämä tutkielma on tapaustutkimus Asoguabon turismiprojektista, ja pohjautuu kuukauden pituiseen kenttätyöhön Ecuadorissa tammikussa 2010 sekä kirjoittajan aiempiin kokemuksiin Asoguabosta. Aineisto koostuu 21 puoli-strukturoidusta laadullisesta haastattelusta kuudentoista informantin kanssa, joista suurin osa oli hyvin läheisesti tekemisissä projektin kanssa. Tämän lisäksi aineistonkeruussa on käytetty havainnointia sekä projektin markkinointimateriaalien sisällönanalyysia. Tutkielma osoittaa reilun turismin projektin sisältävän monia haasteita ennen kuin se voi saavuttaa tavoitteensa tuottaa lisätuloja Asoguabon toimintaan. Tutkimushetkellä projekti hyödytti suoraan pääasiassa muutamia järjestön viljelijöitä, lähinnä niitä, jotka toimivat projektissa oppaina. Nämä oppaat hyötyvät projektista saamalla pieniä lisätuloja, kasvattamalla sosiaalista pääomaansa, sekä saamalla mahdollisuuden oppia muun muassa osallistumalla kursseille. Tutkimuksen keskeiset tulokset osoittavat myös, kuinka vuorovaikutus-ongelmat projektin eri toimijoiden välillä vaikeuttavat tiedonkulkua ja täten reilun turismin toimintaa. Nämä ongelmat myös lisäävät epätietoisuutta Asoguabon muiden viljelijöiden parissa. Lisäksi tutkimus osoittaa, kuinka reilun turismin projektin mainonnassa käytetään osittain samoja keinoja kuin reilun kaupan tuotteiden mainonnassa, joskin tuottajia on kuvattu mainosmateriaaleissa yllättävän vähän ja pääosassa ovat usein eurooppalaiset turistit.