Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy

N-heterocyclic carbenes (NHCs) bind very strongly to transition metals due to their unique electronic structure featuring a divalent carbon atom with a lone pair in a highly directional sp(2)-hybridized orbital. As such, they can be assembled into monolayers on metal surfaces that have enhanced stability compared to their thiol-based counterparts. The utility of NHCs to form such robust self-assembled monolayers (SAMs) was only recently recognized and many fundamental questions remain. Here we investigate the structure and geometry of a series of NHCs on Au(111) using high-resolution X-ray photoelectron spectroscopy and density functional theory calculations. We find that the N-substituents on the NHC ring strongly affect the molecule-metal interaction and steer the orientation of molecules in the surface layer. In contrast to previous reports, our experimental and theoretical results provide unequivocal evidence that NHCs with N-methyl substituents bind to undercoordinated adatoms to form flat-lying complexes. In these SAMs, the donor-acceptor interaction between the NHC lone pair and the undercoordinated Au adatom is primarily responsible for the strong bonding of the molecules to the surface. NHCs with bulkier N-substituents prevent the formation of such complexes by forcing the molecules into an upright orientation. Our work provides unique insights into the bonding and geometry of NHC monolayers; more generally, it charts a clear path to manipulating the interaction between NHCs and metal surfaces using traditional coordination chemistry synthetic strategies

How managers can build trust in strategic alliances: a meta-analysis on the central trust-building mechanisms

Trust is an important driver of superior alliance performance. Alliance managers are influential in this regard because trust requires active involvement, commitment and the dedicated support of the key actors involved in the strategic alliance. Despite the importance of trust for explaining alliance performance, little effort has been made to systematically investigate the mechanisms that managers can use to purposefully create trust in strategic alliances. We use Parkhe’s (1998b) theoretical framework to derive nine hypotheses that distinguish between process-based, characteristic-based and institutional-based trust-building mechanisms. Our meta-analysis of 64 empirical studies shows that trust is strongly related to alliance performance. Process-based mechanisms are more important for building trust than characteristic- and institutional-based mechanisms. The effects of prior ties and asset specificity are not as strong as expected and the impact of safeguards on trust is not well understood. Overall, theoretical trust research has outpaced empirical research by far and promising opportunities for future empirical research exist

New insights into single-molecule junctions using a robust, unsupervised approach to data collection and analysis

We have applied a new, robust and unsupervised approach to data collection, sorting and analysis that provides fresh insights into the nature of single-molecule junctions. Automation of tunneling current-distance (<i>I</i>(<i>s</i>)) spectroscopy facilitates the collection of very large data sets (up to 100 000 traces for a single experiment), enabling comprehensive statistical interrogations with respect to underlying tunneling characteristics, noise and junction formation probability (JFP). We frequently observe unusual low-to-high through-molecule conductance features with increasing electrode separation, in addition to numerous other “plateau” shapes, which may be related to changes in interfacial or molecular bridge structure. Furthermore, for the first time we use the JFP to characterize the homogeneity of functionalized surfaces at the nanoscale

Semi-automatic enrichment of crowdsourced synonymy networks: the WISIGOTH system applied to Wiktionary

International audienceSemantic lexical resources are a mainstay of various Natural Language Processing applications. However, comprehensive and reliable resources are rare and not often freely available. Handcrafted resources are too costly for being a general solution while automatically-built resources need to be validated by experts or at least thoroughly evaluated. We propose in this paper a picture of the current situation with regard to lexical resources, their building and their evaluation. We give an in-depth description of Wiktionary, a freely available and collaboratively built multilingual dictionary. Wiktionary is presented here as a promising raw resource for NLP. We propose a semi-automatic approach based on random walks for enriching Wiktionary synonymy network that uses both endogenous and exogenous data. We take advantage of the wiki infrastructure to propose a validation "by crowds". Finally, we present an implementation called WISIGOTH, which supports our approach

Network organizations of general practitioners: antecedents of formation and consequences of participation

BACKGROUND: Network forms of organization are increasingly popular in primary care. At the end of the 1990s General Practitioners (GPs) in Italy were given the opportunity to adopt network forms of organization with the aim of improving the quality of their services. However factors affecting GPs' choices to join a network and the consequences of network membership have not been evaluated. METHODS: Administrative data of a Local Health Authority in Central Italy were analyzed using statistical methods at individual and dyadic levels of analysis. RESULTS: Homophily factors seem to influence a GP's choice of network. The consequences of network membership on GP performances seem very limited. CONCLUSIONS: When considering to foster the diffusion of network organizational forms in health care creating a network structure, like that of Italian GPs, is not sufficient. Other features of the implementation phase, work organization and human resource management should also be considered

Household networks and emergent territory: a GIS study of Chumash households, villages and rock-art in South-Central California

Elite households of the Californian Chumash have been studied in order to understand the development of Late Holocene hunter-gatherer alliance networks. Equally, models of what has been termed ‘tribelet territories’ have been used to describe land ownership within larger Californian concepts. Surprisingly little research has explicitly addressed issues of how such territories may have developed. In this article, we turn to DeLanda’s philosophy of social complexity to consider how Chumash households may have underpinned the development of tribelet territories and the political implications for their articulation with wider alliances. Importantly, utilizing Geographic Information Systems (GIS), we analyse potential mobility patterns in relation to households, villages and rock-art locales in a case from the Emigdiano Chumash. The results suggest that the painting of rock art was imbricated within processes of territorialization, and that the local placement of art reflects which villages were home to particularly high-status households

Imbalance of flight-freeze responses and their cellular correlates in the Nlgn3-/y rat model of autism

Abstract Background Mutations in the postsynaptic transmembrane protein neuroligin-3 are highly correlative with autism spectrum disorders (ASDs) and intellectual disabilities (IDs). Fear learning is well studied in models of these disorders, however differences in fear response behaviours are often overlooked. We aim to examine fear behaviour and its cellular underpinnings in a rat model of ASD/ID lacking Nlgn3. Methods This study uses a range of behavioural tests to understand differences in fear response behaviour in Nlgn3 −/y rats. Following this, we examined the physiological underpinnings of this in neurons of the periaqueductal grey (PAG), a midbrain area involved in flight-or-freeze responses. We used whole-cell patch-clamp recordings from ex vivo PAG slices, in addition to in vivo local-field potential recordings and electrical stimulation of the PAG in wildtype and Nlgn3 −/y rats. We analysed behavioural data with two- and three-way ANOVAS and electrophysiological data with generalised linear mixed modelling (GLMM). Results We observed that, unlike the wildtype, Nlgn3 −/y rats are more likely to response with flight rather than freezing in threatening situations. Electrophysiological findings were in agreement with these behavioural outcomes. We found in ex vivo slices from Nlgn3 −/y rats that neurons in dorsal PAG (dPAG) showed intrinsic hyperexcitability compared to wildtype. Similarly, stimulating dPAG in vivo revealed that lower magnitudes sufficed to evoke flight behaviour in Nlgn3 −/y than wildtype rats, indicating the functional impact of the increased cellular excitability. Limitations Our findings do not examine what specific cell type in the PAG is likely responsible for these phenotypes. Furthermore, we have focussed on phenotypes in young adult animals, whilst the human condition associated with NLGN3 mutations appears during the first few years of life. Conclusions We describe altered fear responses in Nlgn3 −/y rats and provide evidence that this is the result of a circuit bias that predisposes flight over freeze responses. Additionally, we demonstrate the first link between PAG dysfunction and ASD/ID. This study provides new insight into potential pathophysiologies leading to anxiety disorders and changes to fear responses in individuals with ASD