Mechanochemical Synthesis of N-Aryl Amides from O-Protected Hydroxamic Acids

Two robust and efficient mechanochemical protocols for the synthesis of an array of N-arylamides have been developed. This was achieved by a C-N cross-coupling between O-pivaloyl hydroxamic acids and aryl iodides or aryl boronic acids, in the presence of a stoichiometric amount of a copper mediator. The effectiveness of this method is highlighted by the high-yielding (up to 94%), scalable (up to 8 mmol), and rapid (20 minutes) synthesis of N-aryl amides (15 examples), using a variety of deactivated and sterically encumbered substrates, whilst employing mild conditions and in the absence of solvents. In addition, it was determined that whilst the O-pivaloyl hydroxamic acid precursors can be synthesised mechanochemically, iron contamination originating from the steel jars was found to occur which can hinder the efficacy of this process. Furthermore, 3D printing was used to produce custom milling jars that could successfully accommodate a scaled-up version of the two protocols

Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)

The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand

NMR quantum computation with indirectly coupled gates

An NMR realization of a two-qubit quantum gate which processes quantum information indirectly via couplings to a spectator qubit is presented in the context of the Deutsch-Jozsa algorithm. This enables a successful comprehensive NMR implementation of the Deutsch-Jozsa algorithm for functions with three argument bits and demonstrates a technique essential for multi-qubit quantum computation.Comment: 9 pages, 2 figures. 10 additional figures illustrating output spectr

Robust Ising Gates for Practical Quantum Computation

I describe the use of techniques based on composite rotations to combat systematic errors in controlled phase gates, which form the basis of two qubit quantum logic gates. Although developed and described within the context of Nuclear Magnetic Resonanace (NMR) quantum computing these sequences should be applicable to any implementation of quantum computation based on Ising couplings. In combination with existing single qubit gates this provides a universal set of robust quantum logic gates.Comment: 3 Pages RevTex4 including 2 figures. Will submit to PR

Being fluent and keeping looking

The complexities of the many concepts and models around information literacy are considered, and some personal views given as to how they may best be clarified, both theoretically and practically. A slightly adapted idea of the concept of information fluency can serve as a main general purpose for the promotion of information literacy, expressed as a more specific meta-model for the prevailing technological environment, and as still more specific components for a particular context. The focus of this relatively stable general formulation is on understanding, rather than skills or competences. It can incorporate the need for education, advice and counseling, as well as information provision, and with domain-specific literacies, as well as supporting personal information literacy

Cumulative dyslipidemia with arterial stiffness and carotid IMT progression in asymptomatic adolescents: A simulated intervention longitudinal study using temporal inverse allocation model

Background and aimsWe aimed to examine the longitudinal associations of total cholesterol (TC), non–high-density lipoprotein cholesterol (non–HDL-C), high-density lipoprotein cholesterol (HDL-C), triglyceride, and low-density lipoprotein cholesterol (LDL-C) with carotid-femoral pulse wave velocity (cfPWV) and carotid intima-media thickness (cIMT) progression.MethodsWe studied 1779, 15-year-old participants from the Avon Longitudinal Study of Parents and Children, UK birth cohort, followed up for 9 years. Fasting TC, non–HDL-C, HDL-C, triglyceride, and LDL-C were measured at 15, 17, and 24 years and age-categorized as normal, elevated, and dyslipidemia based on National Heart, Lung, and Blood Institute lipid guidelines. cfPWV and cIMT were measured at 17 and 24 years. Associations were examined using linear mixed-effect models. To simulate the treatment of dyslipidemia we conducted temporal inverse allocation model analyses.ResultsAmong 1779 [49.9% female] participants, mean lipid levels and proportions at elevated or dyslipidemia categories increased from ages 15 through 24 years. Persistently elevated TC: effect estimate 0.026 mm; [95% CI 0.004 to 0.049; p = 0.024], elevated non–HDL-C, and elevated LDL-C were cumulatively associated with cIMT progression. Persistent borderline-low HDL-C: −0.027 mm; [-0.050 to −0.005; p = 0.019] and very-low HDL-C −0.035 mm; [-0.057 to −0.013; p = 0.002] levels were associated with cIMT progression. A temporal inverse allocation of elevated and dyslipidemic levels with normal lipid levels at age 17 years attenuated the associations of cumulative elevated TC, non–HDL-C, LDL-C, and low HDL-C with cIMT progression. Cumulative elevated lipids or dyslipidemia were not associated with cfPWV progression.ConclusionsLate adolescence is key to preventing, halting, and reversing dyslipidemic-related preclinical atherosclerosis progression, warranting universal lipid screening in the general pediatric population.</p

Long-term repetition priming and semantic interference in a lexical-semantic matching task: tapping the links between object names and colors

Using a novel paradigm to engage the long-term mappings between object names and the prototypical colours for objects, we investigated the retrieval of object-colour knowledge as indexed by long-term priming (the benefit in performance from a prior encounter with the same or a similar stimulus); a process about which little is known. We examined priming from object naming on a lexical-semantic matching task. In the matching task participants encountered a visually presented object name (Experiment 1) or object shape (Experiment 2) paired with either a colour patch or colour name. The pairings could either match whereby both were consistent with a familiar object (e.g., strawberry and red) or mismatch (strawberry and blue). We used the matching task to probe knowledge about familiar objects and their colours pre-activated during object naming. In particular, we examined whether the retrieval of object-colour information was modality-specific and whether this influenced priming. Priming varied with the nature of the retrieval process: object-colour priming arose for object names but not object shapes and beneficial effects of priming were observed for colour patches whereas inhibitory priming arose with colour names. These findings have implications for understanding how object knowledge is retrieved from memory and modified by learning

«Малобюджетний» маркетинг

В умовах сьогоднішньої економічної кризи, яка зачепила всі вітчизняні підприємства, та постійного зниження української національної валюти актуальними стають питання пошуку способів економії коштів. Вирішенням таких проблем може стати «мало бюджетний» маркетинг, який допоможе розвиватися підприємству з використанням мінімальної кількості ресурсів. «Малобюджетний» маркетинг – це маркетингові інструменти залучення й утримання клієнтів, які припускають мінімальні витрати, а іноді можна взагалі обійтися без бюджету

Mortality and causes of death in patients with sporadic inclusion body myositis: Survey study based on the clinical experience of specialists in Australia, Europe and the USA

Background: There is a paucity of data on mortality and causes of death (CoDs) in patients with sporadic inclusion body myositis (sIBM), a rare, progressive, degenerative, inflammatory myopathy that typically affects those aged over 50 years. Objective: Based on patient records and expertise of clinical specialists, this study used questionnaires to evaluate physicians’ views on clinical characteristics of sIBM that may impact on premature mortality and CoDs in these patients. Methods: Thirteen physicians from seven countries completed two questionnaires online between December 20, 2012 and January 15, 2013. Responses to the first questionnaire were collated and presented in the second questionnaire to seek elaboration and identify consensus. Results: All 13 physicians completed both questionnaires, providing responses based on 585 living and 149 deceased patients under their care. Patients were reported to have experienced dysphagia (60.2%) and injurious falls (44.3%) during their disease. Over half of physicians reported that a subset of their patients with sIBM had a shortened lifespan (8/13), and agreed that bulbar dysfunction/dysphagia/oropharyngeal involvement (12/13), early-onset disease (8/13), severe symptoms (8/13), and falls (7/13) impacted lifespan. Factors related to sIBM were reported as CoDs in 40% of deceased patients. Oropharyngeal muscle dysfunction was ranked as the leading feature of sIBM that could contribute to death. The risk of premature mortality was higher than the age-matched comparison population. Conclusions: In the absence of data from traditional sources, this study suggests that features of sIBM may contribute to premature mortality and may be used to inform future studies

The Expanding Fireball of Nova Delphini 2013

A classical nova occurs when material accreting onto the surface of a white dwarf in a close binary system ignites in a thermonuclear runaway. Complex structures observed in the ejecta at late stages could result from interactions with the companion during the common envelope phase. Alternatively, the explosion could be intrinsically bipolar, resulting from a localized ignition on the surface of the white dwarf or as a consequence of rotational distortion. Studying the structure of novae during the earliest phases is challenging because of the high spatial resolution needed to measure their small sizes. Here we report near-infrared interferometric measurements of the angular size of Nova Delphini 2013, starting from one day after the explosion and continuing with extensive time coverage during the first 43 days. Changes in the apparent expansion rate can be explained by an explosion model consisting of an optically thick core surrounded by a diffuse envelope. The optical depth of the ejected material changes as it expands. We detect an ellipticity in the light distribution, suggesting a prolate or bipolar structure that develops as early as the second day. Combining the angular expansion rate with radial velocity measurements, we derive a geometric distance to the nova of 4.54 +/- 0.59 kpc from the Sun.Comment: Published in Nature. 32 pages. Final version available at http://www.nature.com/nature/journal/v515/n7526/full/nature13834.htm