All-carbon N-heterocyclic Carbene-catalyzed (3+2) Annulation using Donor-Acceptor Cyclopropanes

Donor-acceptor cyclopropanes are known to serve as dipole precursors capable of engaging in (3+2) annulations with electron-deficient π-systems. In 2013, the reaction of donor-acceptor cyclopropanes with α,β-unsaturated acyl fluorides in an all-carbon (3+2) annulation was discovered. The reaction proceeds in good yields using the IMes NHC to provide diastereomerically pure β-lactone-fused cyclopentanes bearing four contiguous stereocentres. Subsequent studies demonstrated that N-t-butyl substituted homochiral morpholinone NHCs allowed the reaction to be achieved in up to 98 % ee. In this account, a background to this reaction is introduced, along with a complete account of the strengths, limitations and challenges encountered while developing this chemistry.     

The p-hub Model with Hub-catchment Areas,Existing Hubs,and Simulation: A Case Study of Serbian Intermodal Terminals

This paper addresses the problem of optimally locating intermodal freight terminals in Serbia. To solve this problem and determine the effects of the resulting scenarios, two modeling approaches were combined. The first approach is based on multiple-assignment hub-network design, and the second is based on simulation. The multiple-assignment p-hub network location model was used to determine the optimal location of intermodal terminals. Simulation was used as a tool to estimate intermodal transport flow volumes, due to the unreliability and unavailability of specific statistical data, and as a method for quantitatively analyzing the economic, time, and environmental effects of different scenarios of intermodal terminal development. The results presented here represent a summary, with some extension, of the research realized in the IMOD-X project (Intermodal Solutions for Competitive Transport in Serbia).     

Prototype personality diagnosis in clinical practice: A viable alternative for DSM–5 and ICD–11.

Several studies suggest that a prototype-matching approach yields diagnoses of comparable validity to the more complex diagnostic algorithms outlined in the Diagnostic and Statistical Manual of Mental Disorders (4th ed.). Furthermore, clinicians prefer prototype diagnosis of personality disorders to the current categorical diagnostic system or alternative dimensional methods. An important extension of this work was to investigate the degree to which clinicians are able to make prototype diagnoses reliably. The aim of this study was to assess the interrater reliability of a prototype-matching approach to personality diagnosis in clinical practice. Using prototypes derived empirically in prior research, outpatient clinicians diagnosed patients' personality after an initial evaluation period. External evaluators independently diagnosed the same patients after watching videotapes of the same clinical hours. Interrater reliability for prototype diagnosis was high, with a median r = .72. Cross-correlations between disorders were low, with a median r = .01. Clinicians and clinically trained independent observers can assess complex personality constellations with high reliability using a simple prototype-matching procedure, even with prototypes that are relatively unfamiliar to them. In light of its demonstrated reliability, efficiency, and versatility, prototype diagnosis appears to be a viable system for the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders and the 11th edition of the International Classification of Diseases, with exceptional utility for research and clinical practice. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Parking assistance using dense motion-stereo

The ability of generating and interpreting a three-dimensional representation of the environment in real-time is one of the key technologies for autonomous vehicles. While active sensors like ultrasounds have been commercially used, their cost and precision is not favorable. On the other hand, integrating passive sensors, like video cameras, in modern vehicles is quite appealing especially because of their low cost. However, image processing requires reliable real-time algorithms to retrieve depth from visual information. In addition, the limited processing power in automobiles and other mobile platforms makes this problem even more challenging. In this paper we introduce a parking assistance system which relies on dense motion-stereo to compute depth maps of the observed environment in real-time. The flexibility and robustness of our method is showcased with different applications: automatic parking slot detection, a collision warning for the pivoting ranges of the doors and an image-based rendering technique to visualize the environment around the host vehicle. We evaluate the accuracy and reliability of our system and provide quantitative and qualitative results. A comparison to ultrasound and feature-based motion-stereo solutions shows that our approach is more reliable.     

Perceptual bias for affective and nonaffective information in asymmetric Parkinson's disease.

Objective: To relate lateralized impairments of visual perception in Parkinson's disease to asymmetries in the severity of motor symptoms. Method: Ten patients with worse left-sided motor symptoms (LPD), 15 with worse right-sided (RPD), and 13 healthy age-matched controls (all right-handed) viewed mirror-imaged pairs of emotional chimeric faces, (left side smiling, right neutral, and vice versa), of greyscales (strips whose luminance varied smoothly from black on the left to white on the right, and vice versa) and of gender chimeric faces (left side male, right female, and vice versa). Participants signaled which stimulus appeared happier, brighter, or more feminine, respectively, so showing which side received more attention. Results: For emotional chimeras, controls and LPD showed little bias, whereas RPD showed a strong bias to left hemispace (p = .018, r = .45). Across all patients, this bias was associated with severity of right-sided motor impairment (p = .018, r = .49). The bias was much weaker and insignificant for greyscales (p = .72, r = .14). For gender chimeras, RPD again showed a significantly greater left hemispace bias than did LPD (p = .037, r = .47), although neither patient group differed significantly from controls. Across all patients, this bias correlated with ratio of right-to-left symptom severity (p = .044, r = .48). Conclusions: The left hemispace bias in RPD is greater for facial than for luminance judgments, and is amplified for emotional judgments. Asymmetrical degeneration of the striatum, particularly involving the left side, appears to underlie this deficit in visual processing. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Spectral determination of graphs whose components are paths and cycles

We consider the class of graphs each of whose components is either a path or a cycle. We classify the graphs from the class considered into those which are determined and those which are not determined by the adjacency spectrum. In addition, we compare the result with the corresponding results for the Laplacian and the signless Laplacian spectra. It turns out that the signless Laplacian spectrum performs the best, confirming some expectations from the literature.     

The Discovery of Potent Nonstructural Protein 5A (NS5A) Inhibitors with a Unique Resistance Profile—Part 2

In ongoing studies towards novel hepatitis C virus (HCV) therapeutics, inhibitors of nonstructural protein 5A (NS5A) were evaluated. Specifically, starting from previously reported lead compounds, peripheral substitution patterns of a series of biaryl‐linked pyrrolidine NS5A replication complex inhibitors were probed and structure–activity relationships were elucidated. Using molecular modelling and a supercritical fluid chromatographic (SFC) technique, intramolecular H‐bonding and peripheral functional group topology were evaluated as key determinants of activity and membrane permeability. The novel compounds exhibited retained potency as compared with the lead compounds, and also showed promising results against a panel of resistance viruses. Together, the results of the study take us a step closer towards understanding the potency of daclatasvir, a clinical candidate upon which the compounds were based, and to designing improved analogues as second‐generation antiviral agents targeting NS5A.     

Tribological Behavior of Composites Based on ZA-27 Alloy Reinforced with Graphite Particles

The objective of this investigation is to assess the influence of graphite reinforcement on tribological behavior of ZA-27 alloy. The composite with 2 wt% of graphite particles was produced by the compocasting procedure. Tribological properties of unreinforced alloy and composite were studied, using block-on-disk tribometer, under dry and lubricated sliding conditions at different specific loads and sliding speeds. The worn surfaces of the samples were examined by the scanning electron microscopy (SEM). The obtained results revealed that ZA-27/graphite composite specimens exhibited significantly lower wear rate and coefficient of friction than the matrix alloy specimens in all the combinations of applied loads (F _n ) and sliding speeds (v) in dry and lubricated tests. The positive tribological effects of graphite reinforcement of ZA-27 in dry sliding tests were provided by the tribo-induced graphite film on the contact surface of composite. In test conditions, characterized by the small graphite content and modest sliding speeds and applied loads, nonuniform tribo-induced graphite films were formed leading to the increase of the friction coefficient and wear rate, with increase of the sliding speed and applied load. In conditions of lubricated sliding, the very fine graphite particles formed in the contact interface mix with the lubricating oil forming the emulsion with improved tribological characteristics. Smeared graphite decreased the negative influence of F _n on tribological response of composites, what is manifested by the mild regime of the boundary lubrication, as well as by realization of the mixed lubrication at lower values of the v/F _n ratio, with respect to the matrix alloy.     

Use of biomarkers to show sub-cellular effects in meadow voles (Microtus pennsylvanicus) living on an abandoned gold mine site

Run-off from mine tailings ponds constitutes the main anthropogenic release of arsenic in Canada. As a potential consequence, wildlife not normally exposed to arsenic under other circumstances may receive toxicologically relevant concentrations of arsenic compounds in their food and water. To test this hypothesis, and to determine if arsenic is being transported through trophic levels, the arsenic concentrations in members of a short food chain (soil-plant-meadow vole) were measured. Arsenic concentrations were higher in exposed organisms compared with those from a reference location. However, elevated concentrations of arsenic do not necessarily indicate impact, and consequently a biomonitoring study was undertaken to determine if there were sub-cellular effects of exposure in meadow voles (Microtus pennsylvanicus) as a consequence of arsenic exposure. In this work, adenosine triphosphate (ATP) and liver glutathione (GSH) levels were used as biomarkers of exposure and the frequency of red blood cell micronuclei (mono- and polychromatic) was used as a biomarker of effect. ATP results were not conclusive but there was a statistically significant relationship between a reduction of GSH in vole livers and increased liver arsenic concentrations. A statistically significant relationship was also observed between increased micronucleated monochromatic red blood cells in voles from arsenic contaminated sites compared to a background location. The results of the GSH and monochromatic red blood cell investigations suggest that there are possible sub-cellular effects on these voles as a consequence of dietary arsenic exposure. This is the first field study in which such effects have been observed in voles living near mine tailings.