Homogeneous Gold Catalysis through Relativistic Effects: Addition of Water to Propyne

In the catalytic addition of water to propyne the Au(III) catalyst is not stable under non-relativistic conditions and dissociates into a Au(I) compound and Cl2. This implies that one link in the chain of events in the catalytic cycle is broken and relativity may well be seen as the reason why Au(III) compounds are effective catalysts.Comment: 12 pages, 3 figures, 1 tabl

Role of the dielectric constant of ferroelectric ceramic in enhancing the ionic conductivity of a polymer electrolyte composite

The dispersal of high dielectric constant ferroelectric ceramic material Ba(0.7)Sr(0.3)TiO(3) (Tc~30 C) and Ba(0.88)Sr(0.12)TiO(3) (Tc~90 C) in an ion conducting polymer electrolyte (PEO:NH4I) is reported to result in an increase in the room temperature ionic conductivity by two orders of magnitude. The conductivity enhancememt "peaks" as we approach the dielectric phase transition of the dispersed ferroelectric material where the dielectric constant changes from ~ 2000 to 4000. This establishes the role of dielectric constant of the dispersoid in enhancing the ionic conductivity of the polymeric composites.Comment: 10 pages, 2 figure

Homogeneous and heterogenised new gold C-scorpionate complexes as catalysts for cyclohexane oxidation

Gold(III) complexes of type [AuCl2{eta(2)-RC(R'pz)(3)}]Cl [R = R' = H (1), R = CH2OH, R' = H (2) and R = H, R' = 3,5-Me-2(3), pz = pyrazol-1-yl] were supported on carbon materials (activated carbon, carbon xerogel and carbon nanotubes) and used for the oxidation of cyclohexane to cyclohexanol and cyclohexanone, with aqueous H2O2, under mild conditions

Maturation trajectories of cortical resting-state networks depend on the mediating frequency band

The functional significance of resting state networks and their abnormal manifestations in psychiatric disorders are firmly established, as is the importance of the cortical rhythms in mediating these networks. Resting state networks are known to undergo substantial reorganization from childhood to adulthood, but whether distinct cortical rhythms, which are generated by separable neural mechanisms and are often manifested abnormally in psychiatric conditions, mediate maturation differentially, remains unknown. Using magnetoencephalography (MEG) to map frequency band specific maturation of resting state networks from age 7 to 29 in 162 participants (31 independent), we found significant changes with age in networks mediated by the beta (13–30 Hz) and gamma (31–80 Hz) bands. More specifically, gamma band mediated networks followed an expected asymptotic trajectory, but beta band mediated networks followed a linear trajectory. Network integration increased with age in gamma band mediated networks, while local segregation increased with age in beta band mediated networks. Spatially, the hubs that changed in importance with age in the beta band mediated networks had relatively little overlap with those that showed the greatest changes in the gamma band mediated networks. These findings are relevant for our understanding of the neural mechanisms of cortical maturation, in both typical and atypical development.This work was supported by grants from the Nancy Lurie Marks Family Foundation (TK, SK, MGK), Autism Speaks (TK), The Simons Foundation (SFARI 239395, TK), The National Institute of Child Health and Development (R01HD073254, TK), National Institute for Biomedical Imaging and Bioengineering (P41EB015896, 5R01EB009048, MSH), and the Cognitive Rhythms Collaborative: A Discovery Network (NFS 1042134, MSH). (Nancy Lurie Marks Family Foundation; Autism Speaks; SFARI 239395 - Simons Foundation; R01HD073254 - National Institute of Child Health and Development; P41EB015896 - National Institute for Biomedical Imaging and Bioengineering; 5R01EB009048 - National Institute for Biomedical Imaging and Bioengineering; NFS 1042134 - Cognitive Rhythms Collaborative: A Discovery Network

A QM/MM approach for the study of monolayer-protected gold clusters

We report the development and implementation of hybrid methods that combine quantum mechanics (QM) with molecular mechanics (MM) to theoretically characterize thiolated gold clusters. We use, as training systems, structures such as Au25(SCH2-R)18 and Au38(SCH2-R)24, which can be readily compared with recent crystallographic data. We envision that such an approach will lead to an accurate description of key structural and electronic signatures at a fraction of the cost of a full quantum chemical treatment. As an example, we demonstrate that calculations of the 1H and 13C NMR shielding constants with our proposed QM/MM model maintain the qualitative features of a full DFT calculation, with an order-of-magnitude increase in computational efficiency.Comment: Journal of Materials Science, 201

Intellectual Capital Impact on Organizations’ Performance

The abundance of traditional financial evaluation methods reflects historical performances. It is necessary to consider such elements which add value off-balance sheet towards growth. It is argued that there is the difference between book value and market value of a firm, and that difference could be explained by intellectual capital profile. The study is proposed to investigate the impact of six intellectual capital elements human capital, structural capital, customer capital, technology capital, social capital and spiritual capital on the overall performance of the firms. The impactis diagnosed. A developed questionnaire is used to conduct the study. Correlation analysis depicts the data, OLS is used to conduct the analysis

Probabilistic seismic hazard maps for the sultanate of Oman

This study presents the results of the first probabilistic seismic hazard assessment (PSHA) in the framework of logic tree for Oman. The earthquake catalogue was homogenized, declustered, and used to define seismotectonic source model that characterizes the seismicity of Oman. Two seismic source models were used in the current study; the first consists of 26 seismic source zones, while the second is expressing the alternative view that seismicity is uniform along the entire Makran and Zagros zones. The recurrence parameters for all the seismogenic zones were determined using the doubly bounded exponential distribution except the zones of Makran, which were modelled using the characteristic distribution. Maximum earthquakes were determined and the horizontal ground accelerations in terms of geometric mean were calculated using ground-motion prediction relationships developed based upon seismic data obtained from active tectonic environments similar to those surrounding Oman. The alternative seismotectonic source models, maximum magnitude, and ground-motion prediction relationships were weighted and used to account for the epistemic uncertainty. Hazard maps at rock sites were produced for 5 % damped spectral acceleration (SA) values at 0.1, 0.2, 0.3, 1.0 and 2.0 s spectral periods as well as peak ground acceleration (PGA) for return periods of 475 and 2,475 years. The highest hazard is found in Khasab City with maximum SA at 0.2 s spectral period reaching 243 and 397 cm/s[superscript 2] for return periods 475 and 2,475 years, respectively. The sensitivity analysis reveals that the choice of seismic source model and the ground-motion prediction equation influences the results most.Oman Ministerial Cabinet (project number 22409017

Reactivity of Gold Hydrides: O2 Insertion into the Au–H Bond

Dioxygen reacts with the gold(I) hydride (IPr)AuH under insertion to give the hydroperoxide, (IPr)AuOOH, a long-postulated reaction in gold catalysis and the first demonstration of O2 activation by Au-H in a well-defined system. Subsequent condensation gave the peroxide (IPr)Au-OO-Au(IPr) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene). The reaction kinetics are reported, as well as the reactivity of Au(I) hydrides with radical scavengers

Polypyrrole-Fe2O3 nanohybrid materials for electrochemical storage

We report on the synthesis and electrochemical characterization of nanohybrid polypyrrole (PPy) (PPy/Fe2O3) materials for electrochemical storage applications. We have shown that the incorporation of nanoparticles inside the PPy notably increases the charge storage capability in comparison to the “pure” conducting polymer. Incorporation of large anions, i.e., paratoluenesulfonate, allows a further improvement in the capacity. These charge storage modifications have been attributed to the morphology of the composite in which the particle sizes and the specific surface area are modified with the incorporation of nanoparticles. High capacity and stability have been obtained in PC/NEt4BF4 (at 20 mV/s), i.e., 47 mAh/g, with only a 3% charge loss after one thousand cyles. The kinetics of charge–discharge is also improved by the hybrid nanocomposite morphology modifications, which increase the rate of insertion–expulsion of counter anions in the bulk of the film. A room temperature ionic liquid such as imidazolium trifluoromethanesulfonimide seems to be a promising electrolyte because it further increases the capacity up to 53 mAh/g with a high stability during charge–discharge processes