Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Fabrication of material-independent morphology gradients for high-throughput applications

Gradient surfaces allow rapid, high-throughput investigations and systematic studies in many disparate fields, including biology, tribology and adhesion. We describe a novel method for the fabrication of material-independent morphology gradients, involving a two-step process of particle erosion followed by a chemical polishing procedure that preferentially removes features with a small radius of curvature as a function of time. Gradients are fabricated on aluminium surfaces, but they may be readily transferred to other materials via a replication technique, which allows for the production of identical roughness gradient samples with any chosen surface chemistry. The gradients have been characterized by means of scanning electron microscopy and optical profilometry. Standard roughness parameters (Ra, Rq, Rz, Sm and Sk) were calculated from optical profilometry data. The roughness has also been assessed over different wavelength windows by means of a fast Fourier transformation approach.     

Enantioselective hydrogenation of diaryl-substituted α,β-unsaturated nitriles

α,β-Unsaturated nitriles can be hydrogenated with enantioselectivities up to 88% ee using chiral ruthenium-diphenylphosphino bisaryl and bisheteroaryl complexes such as ruthenium(II)-BINAP and ruthenium(II)-BINP. Mechanistic investigations indicate that conversion is accelerated by electron-rich ligands and that an additional coordinative group needs be present in order to promote conversion. The chiral products are useful building blocks for the synthesis of histamine H₂ agonists of the arpromidine type.     

Differential effects of synchronous and asynchronous multifinger coactivation on human tactile performance

Background  

Repeated execution of a tactile task enhances task performance. In the present study we sought to improve tactile performance with unattended activation-based learning processes (i.e., focused stimulation of dermal receptors evoking neural coactivation (CA)). Previous studies show that the application of CA to a single finger reduced the stationary two-point discrimination threshold and significantly increased tactile acuity. These changes were accompanied by an expansion of the cortical finger representation in primary somatosensory cortex (SI). Here we investigated the effect of different types of multifinger CA on the tactile performance of each finger of the right hand.     

A Particle-Mesh Method for the Shallow Water Equations Near Geostrophic Balance

In this paper we outline a new particle-mesh method for rapidly rotating shallow water flows based on a set of regularized equations of motion. The time-stepping method uses an operator splitting of the equations into an Eulerian gravity wave part and a Lagrangian advection part. An essential ingredient is the advection of absolute vorticity by means of translated radial basis functions. We show that this implies exact conservation of enstrophy. The method is tested on two model problems based on the qualitative features of the solutions obtained (i.e., dispersion or smoothness of potential vorticity contours) as well as on the increase in mean divergence level.     

Geometric formulas for Smale invariants of codimension two immersions

We give three formulas expressing the Smale invariant of an immersion f of a (4k−1)-sphere into (4k+1)-space. The terms of the formulas are geometric characteristics of any generic smooth map g of any oriented 4k-dimensional manifold, where g restricted to the boundary is an immersion regularly homotopic to f in (6k−1)-space.The formulas imply that if f and g are two non-regularly homotopic immersions of a (4k−1)-sphere into (4k+1)-space then they are also non-regularly homotopic as immersions into (6k−1)-space. Moreover, any generic homotopy in (6k−1)-space connecting f to g must have at least a_k(2k−1)! cusps, where a_k=2 if k is odd and a_k=1 if k is even.