924 research outputs found

    Inhibition of Alkali Metal Reduction of 1-Adamantanol by London Dispersion Effects

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    A series of alkali metal 1-adamantoxide (OAd1) complexes of formula [M(OAd1)(HOAd1)2], where M=Li, Na or K, were synthesised by reduction of 1-adamantanol with excess of the alkali metal. The syntheses indicated that only one out of every three HOAd1 molecules was reduced. An X-ray diffraction study of the sodium derivative shows that the complex features two unreduced HOAd1 donors as well as the reduced alkoxide (OAd1), with the Ad1 fragments clustered together on the same side of the NaO3 plane, contrary to steric considerations. This is the first example of an alkali metal reduction of an alcohol that is inhibited from completion due to the formation of the [M(OAd1)(HOAd1)2] complexes, stabilized by London dispersion effects. NMR spectroscopic studies revealed similar structures for the lithium and potassium derivatives. Computational analyses indicate that decisive London dispersion effects in the molecular structure are a consequence of the many C−H⋅⋅⋅H−C interactions between the OAd1 groups.Peer reviewe

    Women and Illegal Activities: Gender Differences and Women's Willingness to Comply Over Time

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    In recent years the topics of illegal activities such as corruption or tax evasion have attracted a great deal of attention. However, there is still a lack of substantial empirical evidence about the determinants of compliance. The aim of this paper is to investigate empirically whether women are more willing to be compliant than men and whether we observe (among women and in general) differences in attitudes among similar age groups in different time periods (cohort effect) or changing attitudes of the same cohorts over time (age effect) using data from eight Western European countries from the World Values Survey and the European Values Survey that span the period from 1981 to 1999. The results reveal higher willingness to comply among women and an age rather than a cohort effect. Working Paper 06-5

    Surface Temperature Probability Distributions in the NARCCAP Hindcast Experiment: Evaluation Methodology, Metrics, and Results

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    Methodology is developed and applied to evaluate the characteristics of daily surface temperature distributions in a six-member regional climate model (RCM) hindcast experiment conducted as part of the North American Regional Climate Change Assessment Program (NARCCAP). A surface temperature dataset combining gridded station observations and reanalysis is employed as the primary reference. Temperature biases are documented across the distribution, focusing on the median and tails. Temperature variance is generally higher in the RCMs than reference, while skewness is reasonably simulated in winter over the entire domain and over the western United States and Canada in summer. Substantial differences in skewness exist over the southern and eastern portions of the domain in summer. Four examples with observed long-tailed probability distribution functions (PDFs) are selected for model comparison. Long cold tails in the winter are simulated with high fidelity for Seattle, Washington, and Chicago, Illinois. In summer, theRCMs are unable to capture the distribution width and long warm tails for the coastal location of Los Angeles, California, while long cold tails are poorly realized for Houston, Texas. The evaluation results are repeated using two additional reanalysis products adjusted by station observations and two standard reanalysis products to assess the impact of observational uncertainty. Results are robust when compared with those obtained using the adjusted reanalysis products as reference, while larger uncertainties are introduced when standard reanalysis is employed as reference. Model biases identified in this work will allow for further investigation into associated mechanisms and implications for future simulations of temperature extremes

    Uncertainty in Signals of Large-Scale Climate Variations in Radiosonde and Satellite Upper-Air Temperature Datasets

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    There is no single reference dataset of long-term global upper-air temperature observations, although several groups have developed datasets from radiosonde and satellite observations for climate-monitoring purposes. The existence of multiple data products allows for exploration of the uncertainty in signals of climate variations and change. This paper examines eight upper-air temperature datasets and quantifies the magnitude and uncertainty of various climate signals, including stratospheric quasi-biennial oscillation (QBO) and tropospheric ENSO signals, stratospheric warming following three major volcanic eruptions, the abrupt tropospheric warming of 1976–77, and multidecadal temperature trends. Uncertainty estimates are based both on the spread of signal estimates from the different observational datasets and on the inherent statistical uncertainties of the signal in any individual dataset. The large spread among trend estimates suggests that using multiple datasets to characterize large-scale upperair temperature trends gives a more complete characterization of their uncertainty than reliance on a single dataset. For other climate signals, there is value in using more than one dataset, because signal strengths vary. However, the purely statistical uncertainty of the signal in individual datasets is large enough to effectively encompass the spread among datasets. This result supports the notion of an 11th climate-monitoring principle, augmenting the 10 principles that have now been generally accepted (although not generally implemented) by the climate community. This 11th principle calls for monitoring key climate variables with multiple, independent observing systems for measuring the variable, and multiple, independent groups analyzing the data

    Suited for Success? : Suits, Status, and Hybrid Masculinity

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    This document is the Accepted Manuscript version. The final, definitive version of this paper has been published in Men and Masculinities, March 2017, doi: https://doi.org/10.1177/1097184X17696193, published by SAGE Publishing, All rights reserved.This article analyzes the sartorial biographies of four Canadian men to explore how the suit is understood and embodied in everyday life. Each of these men varied in their subject positions—body shape, ethnicity, age, and gender identity—which allowed us to look at the influence of men’s intersectional identities on their relationship with their suits. The men in our research all understood the suit according to its most common representation in popular culture: a symbol of hegemonic masculinity. While they wore the suit to embody hegemonic masculine configurations of practice—power, status, and rationality—most of these men were simultaneously marginalized by the gender hierarchy. We explain this disjuncture by using the concept of hybrid masculinity and illustrate that changes in the style of hegemonic masculinity leave its substance intact. Our findings expand thinking about hybrid masculinity by revealing the ways subordinated masculinities appropriate and reinforce hegemonic masculinity.Peer reviewe

    Uncertainty in Signals of Large-Scale Climate Variations in Radiosonde and Satellite Upper-Air Temperature Datasets

    Get PDF
    There is no single reference dataset of long-term global upper-air temperature observations, although several groups have developed datasets from radiosonde and satellite observations for climate-monitoring purposes. The existence of multiple data products allows for exploration of the uncertainty in signals of climate variations and change. This paper examines eight upper-air temperature datasets and quantifies the magnitude and uncertainty of various climate signals, including stratospheric quasi-biennial oscillation (QBO) and tropospheric ENSO signals, stratospheric warming following three major volcanic eruptions, the abrupt tropospheric warming of 1976–77, and multidecadal temperature trends. Uncertainty estimates are based both on the spread of signal estimates from the different observational datasets and on the inherent statistical uncertainties of the signal in any individual dataset. The large spread among trend estimates suggests that using multiple datasets to characterize large-scale upperair temperature trends gives a more complete characterization of their uncertainty than reliance on a single dataset. For other climate signals, there is value in using more than one dataset, because signal strengths vary. However, the purely statistical uncertainty of the signal in individual datasets is large enough to effectively encompass the spread among datasets. This result supports the notion of an 11th climate-monitoring principle, augmenting the 10 principles that have now been generally accepted (although not generally implemented) by the climate community. This 11th principle calls for monitoring key climate variables with multiple, independent observing systems for measuring the variable, and multiple, independent groups analyzing the data

    Mechanochemical action of the dynamin protein

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    Dynamin is a ubiquitous GTPase that tubulates lipid bilayers and is implicated in many membrane severing processes in eukaryotic cells. Setting the grounds for a better understanding of this biological function, we develop a generalized hydrodynamics description of the conformational change of large dynamin-membrane tubes taking into account GTP consumption as a free energy source. On observable time scales, dissipation is dominated by an effective dynamin/membrane friction and the deformation field of the tube has a simple diffusive behavior, which could be tested experimentally. A more involved, semi-microscopic model yields complete predictions for the dynamics of the tube and possibly accounts for contradictory experimental results concerning its change of conformation as well as for plectonemic supercoiling.Comment: 17 pages, 4 figures; typos corrected, reference adde
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