609 research outputs found

    Aspects of the coordination chemistry of oxorhenium(V) and oxorhenium(VII) complexes

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    A detailed mechanistic study of ligand exchange reactions was performed on dithiolato-rhenium complexes, MeReO(SCH2C6H 4S)L, (or M-L), where L is a Lewis base; typically a phosphine or pyridine. This study revealed, for incoming ligand Y, that selected ligand exchange reactions appear monophasic while others show biphasic kinetics; these later results indicate the presence of an intermediate. It was determined that the monophasic reactions have an intermediate also, when the first rate constant is made larger by a better leaving group. The rate constants range from 2 x 105 to 1 x 10-4 L mol -1 s-1. For all biphasic reactions, the rate constants have been carefully assigned and both stages have a first-order dependence on the concentration of Y. A common rate constant can be assigned to the second reaction, for a given Y, for a variety of M-L complexes. Spectroscopic evidence shows the intermediate and final product have the same composition. The intermediate is designated MeReO(SCH2C6H4S)Y* and the product MeReO(SCH2C6H4S)Y. The intermediate shows an unusual four bond coupling from the W-pattern of hydrogen and phosphorus. A turnstile mechanism is proposed, to preserve the principle of microscopic reversibility, which requires that the ligands must enter and leave from the same position. Results are also presented from a study of monomerization of the dimeric rhenium species, MeReO(SCH2C6H 4S)2, D, with phosphines of various size and basicity. The results support a mechanism with two intermediates on the pathway to MeReO(SCH2C6H4S)L;Treatment of D with tetrabutylammonium chloride in benzene which has been layered over water yields an ionic dirhenium complex. The complex, [MeReO(SCH2C6H4S)2(mu-OH)] [Bun4N], was found to have a hydroxide ion symmetrically bridging the rhenium atoms, while tetrabutylammonium cation serves as the counter cation for the complex. Results are also presented about how chelating phosphine ligands react with D and M-L complexes;Dialkyl- and diarylsulfoxides are oxidized to sulfones by hydrogen peroxide using methyltrioxorhenium (MTO) as the catalyst. The reaction rate is negligible without a catalyst. The values for the rate constant for the oxygen-transfer step lie in the range 0.1--3 L mol-1 s-1 . The rate constants were significantly smaller than for the oxidation of sulfides to sulfoxides

    Light Dulls and Darkens Bird Eggs

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    Although egg color is generally consistent within individual birds and robust to environmental variation, recent evidence suggests a degree of susceptibility to environmental perturbation or modulation of egg color. Most of this variation manifests via the physiology of the laying female, but some direct impacts of the environment on laid eggs have also been discovered. Here we test whether light changes bird egg color and we quantify its effect, by subjecting variable blue-green eggs of Rüppell\u27s weaver (Ploceus galbula) to a broad-spectrum light source under laboratory conditions, and measuring egg reflectance every few hours. Eggshells gradually decreased in reflectance across the entire measured wavelength spectrum of 250–800 nm. Reflectance peaks were disproportionately affected, such that the height decreased of both the blue-green peak and the smaller UV peak typical of blue-green eggs. The reflectance of lighter eggs was affected slightly more than that of darker eggs. These changes are similar to previous results for changes over long periods of time in darkness, suggesting that light might hasten the same process of pigment degradation that proceeds even without light. Comparison between the experimental light source and both sunlight and typical artificial lighting situations raises the possibility that significant color change might occur during incubation in some birds, but indicates that eggshell illumination in museums for short periods of study is unlikely to affect their color to a detectable extent. Additional research should be performed on eggs of other species and in other light environments, with an eye to an eventual generalized model of the effect of light on eggshell color

    The Impact of Land Use and Human Population Density on Benthic Macroinvertebrate Diversity in a Highly Urbanized River

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    Many studies have documented the detrimental effects of urbanization on aquatic ecosystems. What is less known is how “super urban” centers—areas with unusually high human population densities and immense infrastructures—impact biodiversity. Specifically, freshwater streams and rivers that are situated in highly urbanized metropolitan areas might be more susceptible to anthropogenic disturbance. Here, we evaluated the impacts of land use and human population density on benthic macroinvertebrate diversity along the Bronx River, a freshwater river situated in one of the largest urban centers in the world: the New York metropolitan area. We addressed the following research question: How does (1) high intensity development, (2) distance to the Bronx River Parkway, and (3) human population density impact benthic macroinvertebrate diversity along the Bronx River? To answer this question, we sampled benthic macroinvertebrates from 18 study sites, and calculated five measures of benthic macroinvertebrate diversity: (1) family richness, (2) Ephemeroptera-Plecoptera-Trichoptera (EPT) family richness, (3) Simpson’s diversity index, (4) invasive species abundance, and (5) family dominance. Our study yielded three main results. First, benthic macroinvertebrate diversity was extremely low. Across study sites, family richness ranged from two to seven and EPT family richness ranged from zero to one. Indeed, only four of 18 sites harbored pollution-sensitive mayflies (Ephemeroptera) or caddisflies (Trichoptera), and zero sites supported stoneflies (Plecoptera). Second, two measures of land use, high intensity development (80 to 100% impervious surface cover) and distance to a major highway (Bronx River Parkway) were associated with reduced biodiversity. Specifically, high intensity development was negatively associated with family richness and Simpson’s diversity, and positively associated with invasive species abundance. Study sites located closer to the Bronx River Parkway harbored more invasive species than study sites located further away. One invasive species, the Asian clam (Corbicula fluminea), was the second most dominant taxon on the Bronx River. Finally, we found that high human population density was negatively associated with family richness and positively associated with invasive species abundance. Our results suggest that “super urban” centers are especially vulnerable to anthropogenic pressures and that large urban areas warrant special attention for mitigating the decline of benthic macroinvertebrates

    Environmental applications of airborne geophysics: groundwater and contaminated soil in Finland, Germany and United Kingdom

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    The use of airborne geophysical data for environmental studies started in GTK already in the l970’s but came into common use only in the late l990’s. In recent years airborne data have been used successfully especially in environmental studies related to old mines and old mining districts, groundwater and soil contamination. This paper presents five studies where GTK's airborne data have been successfully applied for environmental and groundwater investigation purposes. In the section “Airborne methods in groundwater studies in Finland" Heikki Vanhala and Annina Mattsson discuss the use of airborne electromagnetic(AEM). magnetic and radiometric data for studying bedrock aquifers and groundwater related to glaciofluvial formations. Jouni Lerssi presents a case “Mapping a waste-water pond — a case from Lievestuore, central Finland", in which AEM data were used for mapping and characterising a large wastewater (sodium lignosulphonate) pond and its surroundings. An example of site monitoring using airborne data is given by Mari Lahti. Her contribution “Landfill monitoring at Ammassuo, southern Finland" is based on airborne measurements conducted in 1984, 1993, 1997 and 1999 over the Ammassuo municipal landfill. The contribution related to abandoned mines “Mapping the environmental risks of a wide contamination site ~ results from a mining region in eastern Germany“, by Mari Lahti, discusses the use of airborne gamma-ray surveys in mapping an old uranium mining district and in monitoring radiation levels. She also presents a case of integrated use of radiometric and magnetic data in mapping an old black coal mining area and a case of the combined use of magnetic and ground resistivity data for mapping impacts of nickel mining and smelting. The last contribution "Environmental applications of the GTK AEM data in the UK", by David Beamish, is based on AEM data from four areas in the East Midlands, in the UK. Two sites, the area of the Thoresby coal mine and municipal landfills in the Langar area, are discussed in detail

    Health and Well-being

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    Non peer reviewe

    Treatment of alcohol dependence in patients with co-morbid major depressive disorder – predictors for the outcomes with memantine and escitalopram medication

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    <p>Abstract</p> <p>Background</p> <p>Alcohol dependence comorbid with major depressive disorder poses a major challenge in the clinical setting. The results in the treatment with selective serotonin re-uptake inhibitors have been conflicting. Thus, we compared in alcohol-dependent patients with co-morbid major depressive disorder the selective serotonin re-uptake inhibitor escitalopram to a compound that acts on different transporter system and may reduce craving, the glutamate receptor antagonist memantine.</p> <p>Methods</p> <p>Eighty alcohol-dependent patients comorbid with major depressive disorder in municipal alcohol clinics were randomized 1:1 to receive memantine 20 mg or escitalopram 20 mg in a double-blind manner. During the 26-week study period patients continued their routine treatment at the clinics. Abstinence was not required but encouraged. The patients attended visits weekly during the first month, and then at 3 and at 6 months. Outcome measures were Alcohol Use Disorders Identification Test (AUDIT), Obsessive Compulsive Drinking Scale (OCDS) and Drinking Diary.</p> <p>Results</p> <p>The completion rate was high in both groups, especially among the patients who had been abstinent at the beginning of the study. However, among those patients who were not abstinent at baseline, 47% in both groups discontinued the study. Numbers of abstinent days were high in both groups throughout the study. Alcohol consumption measured by the AUDIT QF (quantity-frequency) score was significantly reduced in both groups, as was the craving for alcohol measured by the OCDS. Early age at first alcohol intoxication predicted poor treatment outcomes in patients treated with escitalopram, and the same was seen with the early onset of the first depressive episode. The same predictive effects were not found in patients treated with memantine.</p> <p>Conclusion</p> <p>Our results indicate that both memantine and escitalopram are useful adjunct medications for the treatment of alcohol dependence co-morbid with major depression. Memantine was at least as effective with regard to drinking as escitalopram. We believe that a direct comparison of memantine, with the commonly used escitalopram, can provide useful information for clinicians on the treatment of alcohol dependency co-morbid with MDD.</p> <p>Trial registration</p> <p>ClinicalTrials.gov Identifier # NCT00368862</p

    Citizenship and Socio-Political Integration: A Person-Oriented Analysis Among Russian-Speaking Minorities in Estonia, Finland and Norway

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    This survey study utilized a person-oriented approach to explore the patterns of socio-political integration among Russian-speaking minority group members in three neighboring countries in the Baltic area: Estonia (n = 482), Finland (n = 252), and Norway (n = 215). Three profiles were obtained in all countries: critical integration, separation, and assimilation. In the whole sample, critical integration was the most common acculturation profile. After the profiles were established, they were examined vis-a-vis citizenship and integration context to see, whether and to what extent, the objective (i.e., citizenship) and subjective (i.e., perceived social status and sense of belonging) socio-political integration of Russian-speakers corresponded with each other. Critical integration and separation were the most common profiles among participants holding national citizenship of the country of residence, while foreign citizenship was not related to any specific profile. Separation was rare among participants holding dual citizenship, but it was the most common profile among participants with undetermined citizenship. Also, intergroup context was associated with socio-political integration: critical integration and separation were the most common profiles of Russian-speakers in Estonia, critical integration and assimilation profiles in Finland, and assimilation profile in Norway. The results are discussed in relation to previous variable-oriented research and official integration policies of the countries studied.Peer reviewe

    When Psychological Contract Is Violated : Revisiting the Rejection-Disidentification Model of Immigrant Integration

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    In this study, we investigated how perceived ethnic discrimination is related to attitudes towards the national majority group and willingness to confront injustice to promote the social standing of a minority group. We examined this relationship via two mediating factors; national (dis)identification from and out-group (dis)trust of the national majority group. The Rejection-Disidentification Model (RDIM) was refined, first, to account for willingness to confront injustice as a consequence of perceived rejection, and second, intergroup (dis)trust was examined as an additional mediating mechanism that can explain attitudinal and behavioural reactions to perceived rejection simultaneously with national disidentification. The model was tested in a comparative survey data of Russian-speaking minority in Estonia (N = 482), Finland (N = 254), and Norway (N = 219). In all three countries, the more Russian-speakers identified as Russians and the more they perceived ethnic discrimination, the more negative were their attitudes toward the national majority groups and the more willing they were to engage in action to confront group-based injustice. Whereas disidentification from and distrust of national majority group accounted for the discrimination-attitude link to a large extent, both factors had demobilizing effects on willingness to confront injustice, making Russian-speaking immigrants more passive but hostile. The findings are discussed in relation to the risks involved in politicization of immigrants struggling with perceived inequalities.Peer reviewe
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