Quantification of Noncovalent Interactions in Azide–Pnictogen, –Chalcogen,and –Halogen Contacts

The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from −1.00 to −5.5 kcal mol⁻¹.     

Intramolecular trans‐Dicarbofunctionalization of Alkynes by a Formal anti‐Carbopalladation/Stille Cascade

An intramolecular Pd‐catalyzed trans‐dicarbofunctionalization of internal alkynes using aryl bromides and aryl stannanes is presented. Tetrasubstituted double bonds embedded in an oligocyclic ring system are obtained in a regio‐ and diastereoselective fashion. The transformation features a broad substrate scope and functional‐group tolerance.     

Interactions Between Flame Topology and Turbulent Transport in High-Pressure Premixed Combustion

Flow, Turbulence and Combustion - Direct numerical simulations of a turbulent premixed stoichiometric methane-oxygen flame were conducted. The chosen combustion pressure was 20 bar, to...     

Nickel‐Catalyzed Cross‐Electrophile Coupling with Organic Reductants in Non‐Amide Solvents

Cross‐electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non‐amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron‐poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to ‘hold’ a reaction without diminishing yield or catalyst activity.     

Designing and using professional development resources for inquiry-based learning

This paper describes an attempt to design, analyse and refine professional development (PD) resources that encourage the implementation of inquiry-based learning (IBL). We describe the iterative development of the resources in England with over 100 mathematics teachers from secondary, tertiary and adult education and then analyse the impact these resources had on teachers’ beliefs and practices and the issues arising. This evaluation revealed that teachers had moved away from transmission-based orientations, encouraged by the use of less structured tasks and sample lesson plans, but some found it difficult to adopt IBL pedagogies. The most significant issues for teachers may be summarised as: confusing IBL with ‘discovery’ learning; developing and managing collaborative cultures within the classroom; and planning lessons that adapt to the emerging needs of learners.     

Synchrotron radiation analysis in the study of pollution in the ring‐billed gull (larus delawarensis): a novel application of the technique

Synchrotron radiation analysis is a powerful tool for identifying pollutants. Here, we explore the distribution of elements in the flight feathers of ring‐billed gulls, Larus delawarensis, to identify potential pollutants and their distribution throughout the feather. Our analysis using Synchrotron Radiation Analysis and Environmental Scanning Electron Microscopy has identified a variety of metals that are integral parts of the feather structure including: calcium (Ca), strontium (Sr), zinc (Zn) and iron (Fe). The darker portions of the flight feather were enriched with Zn and Fe, which supports the suggestion that feather melanins are efficient ligands of some metals found in the environment, sequestering potentially harmful particles away from the body. However, trace lead (Pb) acquired from the regional pollution was detected only in females, and it was distributed across both the melanized and non‐melanized portions of the feather suggesting that only some metals are efficiently sequestered by melanins. Overall this study highlights a potential method for identifying pollutants using bird feathers, which has broader implications on environmental sensing as well as avian and human health. Copyright © 2013 John Wiley & Sons, Ltd.