Reactions of [NH3+·, H2O] with carbonyl compounds: a McLafferty rearrangement within a complex?

AbstractThe reactions of the water solvated ammonia radical cation [NH3·+, H2O] with a variety of aldehydes and ketones were investigated. The reactions observed differ from those of low energy aldehydes and ketones radical cations, although electron transfer from the keto compound to ionized ammonia is thermodynamically allowed within the terbody complexes initially formed. The main process yields an ammonia solvated enol with loss of water and an alkene. This process corresponds formally to a McLafferty fragmentation within a complex. With aldehydes, another reaction can take place, namely the transfer of the hydrogen from the CHO group to ammonia, leading to the proton bound dimer of ammonia and water, and to the NH4+ cation. Comparison between the available experimental results leads to the conclusion that the McLafferty fragmentation occurs within the terbody complex initially formed, with no prior ligand exchange, the water molecule acting as a spectator partner

Bessel Process and Conformal Quantum Mechanics

Different aspects of the connection between the Bessel process and the conformal quantum mechanics (CQM) are discussed. The meaning of the possible generalizations of both models is investigated with respect to the other model, including self adjoint extension of the CQM. Some other generalizations such as the Bessel process in the wide sense and radial Ornstein- Uhlenbeck process are discussed with respect to the underlying conformal group structure.Comment: 28 Page

Utilizing image texture to detect land-cover change in Mediterranean coastal wetlands

Land-use/cover change dynamics were investigated in a Mediterranean coastal wetland. Change Vector Analysis (CVA) without and with image texture derived from the co-occurrence matrix and variogram were evaluated for detecting land-use/cover change. Three Landsat Thematic Mapper (TM) scenes recorded on July 1985, 1993 and 2005 were used, minimizing change detection error caused by seasonal differences. Images were geometrically, atmospherically and radiometrically corrected. CVA without and with texture measures were implemented and assessed using reference images generated by object-based supervised classification. These outputs were used for cross-classification to determine the ‘from–to’ change used to compare between techniques. The Landsat TM image bands together with the variogram yielded the most accurate change detection results, with Kappa statistics of 0.7619 and 0.7637 for the 1985–1993 and 1993–2005 image pairs, respectively

The effects of shoulder load and pinch force on electromyographic activity and blood flow in the forearm during a pinch task

The object of the current study was to determine whether static contraction of proximal musculature has an effect on the blood flow more distally in the upper extremity. Static contractions of muscles in the neck shoulder region at three levels (relaxed, shoulders elevated and shoulders elevated loaded with 4.95 kg each) were combined with intermittent pinch forces at 0, 10 and 25% of the maximum voluntary contraction (MVC). Blood flow to the forearm was measured with Doppler ultrasound. Myoelectric activity of the forearm and neck-shoulder muscles was recorded to check for the workload levels. Across all levels of shoulder load, blood flow increased significantly with increasing pinch force (21% at 10% MVC and by 44% at 25% MVC). Blood flow was significantly affected by shoulder load, with the lowest blood flow at the highest shoulder load. Interactions of pinch force and shoulder load were not significant. The myoelectric activity of forearm muscles increased with increasing pinch force. The activation of the trapezius muscle decreased with increasing pinch force and increased with increasing shoulder load. The precise mechanisms accounting for the influence of shoulder load remains unclear. The results of this study indicate that shoulder load might influence blood flow to the forearm

IgE allergy diagnostics and other relevant tests in allergy, a World Allergy Organization position paper

Currently, testing for immunoglobulin E (IgE) sensitization is the cornerstone of diagnostic evaluation in suspected allergic conditions. This review provides a thorough and updated critical appraisal of the most frequently used diagnostic tests, both in vivo and in vitro. It discusses skin tests, challenges, and serological and cellular in vitro tests, and provides an overview of indications, advantages and disadvantages of each in conditions such as respiratory, food, venom, drug, and occupational allergy. Skin prick testing remains the first line approach in most instances; the added value of serum specific IgE to whole allergen extracts or components, as well as the role of basophil activation tests, is evaluated. Unproven, non-validated, diagnostic tests are also discussed. Throughout the review, the reader must bear in mind the relevance of differentiating between sensitization and allergy; the latter entails not only allergic sensitization, but also clinically relevant symptoms triggered by the culprit allergen

25 Years of Self-organized Criticality: Concepts and Controversies

Introduced by the late Per Bak and his colleagues, self-organized criticality (SOC) has been one of the most stimulating concepts to come out of statistical mechanics and condensed matter theory in the last few decades, and has played a significant role in the development of complexity science. SOC, and more generally fractals and power laws, have attracted much comment, ranging from the very positive to the polemical. The other papers (Aschwanden et al. in Space Sci. Rev., 2014, this issue; McAteer et al. in Space Sci. Rev., 2015, this issue; Sharma et al. in Space Sci. Rev. 2015, in preparation) in this special issue showcase the considerable body of observations in solar, magnetospheric and fusion plasma inspired by the SOC idea, and expose the fertile role the new paradigm has played in approaches to modeling and understanding multiscale plasma instabilities. This very broad impact, and the necessary process of adapting a scientific hypothesis to the conditions of a given physical system, has meant that SOC as studied in these fields has sometimes differed significantly from the definition originally given by its creators. In Bak’s own field of theoretical physics there are significant observational and theoretical open questions, even 25 years on (Pruessner 2012). One aim of the present review is to address the dichotomy between the great reception SOC has received in some areas, and its shortcomings, as they became manifest in the controversies it triggered. Our article tries to clear up what we think are misunderstandings of SOC in fields more remote from its origins in statistical mechanics, condensed matter and dynamical systems by revisiting Bak, Tang and Wiesenfeld’s original papers