Iodoarene-Catalyzed Cyclizations of Unsaturated Amides

The cyclization of N-alkenylamides catalyzed by iodoarenes under oxidative conditions is presented. Five-, six-, and seven-membered rings with a range of substitutions can be prepared by this route. Preliminary data from the use of chiral iodoarenes as precatalysts show that enantiocontrol is feasible

Dynamical modeling of collective behavior from pigeon flight data: flock cohesion and dispersion

Several models of flocking have been promoted based on simulations with qualitatively naturalistic behavior. In this paper we provide the first direct application of computational modeling methods to infer flocking behavior from experimental field data. We show that this approach is able to infer general rules for interaction, or lack of interaction, among members of a flock or, more generally, any community. Using experimental field measurements of homing pigeons in flight we demonstrate the existence of a basic distance dependent attraction/repulsion relationship and show that this rule is sufficient to explain collective behavior observed in nature. Positional data of individuals over time are used as input data to a computational algorithm capable of building complex nonlinear functions that can represent the system behavior. Topological nearest neighbor interactions are considered to characterize the components within this model. The efficacy of this method is demonstrated with simulated noisy data generated from the classical (two dimensional) Vicsek model. When applied to experimental data from homing pigeon flights we show that the more complex three dimensional models are capable of predicting and simulating trajectories, as well as exhibiting realistic collective dynamics. The simulations of the reconstructed models are used to extract properties of the collective behavior in pigeons, and how it is affected by changing the initial conditions of the system. Our results demonstrate that this approach may be applied to construct models capable of simulating trajectories and collective dynamics using experimental field measurements of herd movement. From these models, the behavior of the individual agents (animals) may be inferred

THE THREE-DIMENSIONAL EVOLUTION OF ION-SCALE CURRENT SHEETS: TEARING AND DRIFT-KINK INSTABILITIES IN THE PRESENCE OF PROTON TEMPERATURE ANISOTROPY

We present the first three-dimensional hybrid simulations of the evolution of ion-scale current sheets, with an investigation of the role of temperature anisotropy and associated kinetic instabilities on the growth of the tearing instability and particle heating. We confirm the ability of the ion cyclotron and firehose instabilities to enhance or suppress reconnection, respectively. The simulations demonstrate the emergence of persistent three-dimensional structures, including patchy reconnection sites and the fast growth of a narrow-band drift-kink instability, which suppresses reconnection for thin current sheets with weak guide fields. Potential observational signatures of the three-dimensional evolution of solar wind current sheets are also discussed. We conclude that kinetic instabilities, arising from non-Maxwellian ion populations, are significant to the evolution of three-dimensional current sheets, and two-dimensional studies of heating rates by reconnection may therefore over-estimate the ability of thin, ion-scale current sheets to heat the solar wind by reconnection

Solar Wind Turbulence and the Role of Ion Instabilities

International audienc

Synthesis of quaternary aryl phosphonium salts: photoredox-mediated phosphine arylation

We report a synthesis method for the construction of quaternary aryl phoshonium salts at ambient temperature. The regiospecific reaction invovles the coupling of phosphines with aryl radicals derived from diaryliodonium salts under photoredox conditions

Large-Eddy Simulations of Magnetohydrodynamic Turbulence in Heliophysics and Astrophysics

We live in an age in which high-performance computing is transforming the way we do science. Previously intractable problems are now becoming accessible by means of increasingly realistic numerical simulations. One of the most enduring and most challenging of these problems is turbulence. Yet, despite these advances, the extreme parameter regimes encountered in space physics and astrophysics (as in atmospheric and oceanic physics) still preclude direct numerical simulation. Numerical models must take a Large Eddy Simulation (LES) approach, explicitly computing only a fraction of the active dynamical scales. The success of such an approach hinges on how well the model can represent the subgrid-scales (SGS) that are not explicitly resolved. In addition to the parameter regime, heliophysical and astrophysical applications must also face an equally daunting challenge: magnetism. The presence of magnetic fields in a turbulent, electrically conducting fluid flow can dramatically alter the coupling between large and small scales, with potentially profound implications for LES/SGS modeling. In this review article, we summarize the state of the art in LES modeling of turbulent magnetohydrodynamic (MHD) ows. After discussing the nature of MHD turbulence and the small-scale processes that give rise to energy dissipation, plasma heating, and magnetic reconnection, we consider how these processes may best be captured within an LES/SGS framework. We then consider several special applications in heliophysics and astrophysics, assessing triumphs, challenges,and future directions