Language performance in bilingual patients with neurodegenerative dementia: Preservation of first language?

Nowadays, many people use several languages in their everyday life. As a result, a lot of patients with neurodegenerative dementia are bilingual. This raises complex questions regarding language impairment in this population and how best to assess and rehabilitate it. Cerebral representation of languages and language impairment in bilinguals has become an interesting topic of research. In this study, we assessed 21 late-bilinguals patients with dementia and compared their results to 19, cognitively healthy, matched controls to study L1 preservation. Our results suggest that L1 is not better preserved in patients with neurodegenerative dementia. Interestingly, we demonstrated a better preservation of comprehension in L2 in our global population, regardless of the dementia. This points to the role of immersion in language preservation

N-heterocyclic carbene ligands for iridium-catalysed asymmetric hydrogenation

The general objective of this research work was to investigate the potential of N-heterocyclic carbenes as ligands for the asymmetric iridium-catalysed hydrogenation of olefins and imines. In this context, efficient synthetic routes were developed to access three new classes of NHC-based ligands. The first class consists of chiral monodentate C2-symmetric NHCs which are combined with two different co-ligands, pyridine or triphenylphosphine, in order to give rise to direct analogues of Crabtree's catalyst. In the second class, the NHC is tethered to a chiral oxazoline unit and forms a six-membered-chelate ring upon complexation. Finally, the third class of ligands consists of bidentate ligands, in which the NHC is linked to either a phosphine or a phosphinite moiety. Analogues of Crabtree’s catalyst bearing a chiral C2-symmetric NHC: Six iridium complexes, analogues of Crabtree's catalyst bearing monodentate NHCs, were synthesised starting from readily available enantiopure C2-symmetric imidazolium salts (Figure 5.1). Characterisation by crystallographic studies and 2D NMR gave insight into the geometry of the complexes and their dynamic behaviour. The catalytic activity of these new iridium complexes was tested in the enantioselective hydrogenation of a range of unfunctionalised olefins. Full conversion of trisubstituted olefins was only obtained under forcing conditions (50 bar H2, 100C°, 16h). Higher activities were measured for terminal olefin 73, which was fully hydrogenated in 2 hours at room temperature and 50 bar H2. The low enantioselectivities observed overall (up to 44%) are probably due to the lack of rigidity of such compounds compared to chelate complexes. Oxazoline-NHC ligands: Two sets of oxazoline-NHC iridium complexes 81a-f and 90a-o were synthesised (Figure 5.2). Simple and efficient syntheses, which enable easy variation of the ligand substituents, were developed for both classes. X-ray data analysis of one compound from each library confirmed that the electronic properties of the iridium are similar to those observed in Ir-P,N complexes. Complexes 81a-f and 90a-o were successfully tested in the asymmetric hydrogenation of unfunctionalised olefins. The high asymmetric inductions obtained (ee value up to 90% with trans-α-methylstilbene) were attributed to the rigidity generated by the six-membered chelate ring. Despite the wide range of catalysts investigated, the enantiomeric excesses measured with our two families did not compete with the most efficient Ir-P,N complexes. Phosphine/phosphinite-NHC ligands: Three new iridium phosphine-NHC complexes 121a-c (R1 = Me, iPr and mesityl) were synthesised and fully characterised by X-ray diffraction studies and 2D NMR analysis (Figure 5.3). An efficient four step synthesis was developed from 2-phenyl oxirane, giving access to iridium complex 131. The electronic properties of the two types of iridium complexes were investigated by X-ray analyses and NMR studies. In contrast to Ir-P,N and oxazoline-NHC complexes, almost no difference of the trans influence exerted on the two cod double bonds was observed. The four complexes were tested in the enantioselective hydrogenation of olefins. Low conversion values were measured in the hydrogenation of unfunctionalised olefins. However, promising activities (approximate TOF value of 400 h-1) were found when functionalised substrates such as allylic alcohol and imines were hydrogenated. The moderate enantioselectivities measured throughout the screen are thought to originate from the lack of rigidity of the two types of complexes, which display conformers at room temperature as shown by 2D NMR analyses

Explore the Complaint Towards Street Vendors in Manhattan: Discussion About Distribution and Influential Factors

The informal economy, represented by the street vendors, is not a recent trend. Although there are a lot of advantages of the street vendors, conflicts exist. This research explores the complaints towards street vendors in Manhattan and discusses their distribution and influential factors. Through the analysis, governments and city planners have a general understanding of the conflicts and guideline for the future design and regulation. It mainly uses the quantitative method, by a mix of data, to explore the complaints towards street vendors. This includes the spatial analysis using GIS and the linear regression model. The results show that the more diverse that the land use is, the more conflicts between the street vendors and the city. The larger the income unevenness, the more complaints. And the area with more street connectivity has more complaints towards street vendors. The results reevaluate the mixed land use in urban planning and the current regulation

Assistante sociale et militante, une évidence ?: l'engagement militant comme compétence de la pratique professionnelle des assistantes sociales

Pour la plus grande majorité, travail social et militantisme sont associés. Mais alors, pourquoi l’engagement militant est-il si peu visible dans la formation d’assistante sociale comme dans la profession ? Est-ce une notion qui, au fil des années, s’est gentiment éteinte dans le milieu du travail social ou est-ce les professionnelles qui ne ressentent plus la nécessité d’être militantes ? Aujourd’hui, de nombreuses professionnelles de service social se plaignent des conditions de travail ou des conditions sociales et financières des bénéficiaires. Les services sont surchargés et les assistantes sociales en souffrance. A partir de ces constatations, ne faudrait-il pas envisager de repenser la formation ainsi que le métier d’assistante sociale

Accurate measurement of residual dipolar couplings in anisotropic phase

The determination of residual dipolar couplings (RDCs) by quantitative J spectroscopy methods such as Heteronuclear Single Quantum Correlation with Phase Encoded Coupling (HSQC-PEC) is prone to systematic errors that may be caused by differential attenuation during the conversion of orthogonal density operator components into observable terms. The attenuation may be caused by miscalibration of radio-frequency pulses and by relaxation effects. A simple method is presented that allows one to remove most of these systematic errors without losses in sensitivity or resolutio

Swissness bei SWISS : eine Analyse des Potenzials des Co-Branding mit der Marke Schweiz bei der Schweizer Fluggesellschaft Swiss International Air Lines

Mit steigendem Konkurrenzkampf im internationalen Umfeld nimmt Branding auch bei Fluggesellschaften einen immer wichtigeren Stellenwert ein. Trotz der Popularität des Co-Branding mit der Ländermarke Schweiz wurde anhin wenig zum Mehrwert von Swissness in der Flugbranche untersucht. In dieser Arbeit wird die potenzielle Wertsteigerung des Co-Branding mit der Marke Schweiz bei der Schweizer Fluggesellschaft Swiss International Air Lines eruiert. Nach einem theoretischen Überblick zum Corporate Branding, dem Co-Branding mit der Ländermarke sowie dem Branding in der Flugbranche wird anhand einer Methodentriangulation – bestehend aus einem Experteninterview, einer qualitativen Inhaltsanalyse sowie Fokusgruppen – der potenzielle Mehrwert des Co-Branding mit der Marke Schweiz bei SWISS empirisch beleuchtet. Die Ergebnisse zeigen, dass Swissness teilweise einen Mehrwert bietet, denn dadurch werden Unternehmenswerte wie Qualität, Zuverlässigkeit und Luxus positiv akzentuiert. Jedoch legen sie auch den Schluss nahe, dass neben dem Co-Branding eine emotionale Ansprache und ein verstärkter Fokus auf die individuellen Kundenbedürfnisse ebenso zur Wertesteigerung der Marke SWISS beitragen.In increasingly competitive markets, branding is of growing interest to airline companies. Despite an increased interest in co-branding with the country Switzerland, little has been investigated in the added value that co-branding with the county-of-origin plays when branding the national carrier of Switzerland Swiss International Air Lines. This paper set out to investigate the potential of co-branding the airline SWISS with the country brand Switzerland. After an overview of the theoretical framework to corporate branding, co-branding with the country-of-origin as well as branding in the airline industry has been given, the empirical research is conducted consisting of an expert interview, a qualitative content analysis and focus groups. As the results show, Swissness does, to some extent, influence the brand SWISS in a positive way. Core brand values such as quality, reliability and luxury are emphasized through co-branding. However, the results indicate that other factors such as emotionality and a stronger customer focus also add to the value of the brand SWISS

Understanding the role of oxygen-vacancy defects in Cu₂O(111) from first-principle calculations

The presence of defects, such as copper and oxygen vacancies, in cuprous oxide films determines their characteristic carrier conductivity and consequently their application as semiconducting systems. There are still open questions on the induced electronic re-distribution, including the formation of polarons. Indeed, to accurately reproduce the structural and electronic properties at the cuprous oxide surface, very large slab models and theoretical approaches that go beyond the standard generalized gradient corrected density functional theory are needed. In this work we investigate oxygen vacancies formed in proximity of a reconstructed Cu$_{2}$O(111) surface, where the outermost unsaturated copper atoms are removed, thus forming non-stoichiometric surface layers with copper vacancies. We address simultaneously surface and bulk properties by modelling a thick and symmetric slab, to find that hybrid exchange-correlation functionals are needed to describe the oxygen vacancy in this system. Our simulations show that the formation of oxygen vacancies is favoured in the sub-surface layer. Moreover, the oxygen vacancy leads to a splitting and left-shift of the shallow hole states in the gap, which are associated with the deficiency of copper at the surface. These findings suggest that surface electronic structure and reactivity are sensitive to the presence of oxygen vacancies, also when the latter are formed deeper within the film