The adsorption of a substituted benzene,the ethynyl-trifluoro-toluene on Si(100)-2 × 1

The adsorption of 3-ethynyl-trifluoro-toluene (ETFT) on Si(100)-2 × 1 surface in ultra high vacuum is studied in the low coverage regime, through a joint experimental and theoretical approach. The STM images of both filled and empty states revealed few distinct adsorption configurations. On the basis of Density Functional Theory (DFT) calculations the STM images were simulated and three main adsorption configurations were identified, with a predominance of di-sigma bonded species that leave the benzene ring unreacted. A discussion of the reactivity of the reconstructed silicon surface towards benzene derivatives is proposed by comparing the adsorption of ETFT close related molecules, like styrene and phenylacetylene.     

Divergent Synthesis of Bioactive Dithiodiketopiperazine Natural Products Based on a Double C(sp3)−H Activation Strategy

This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (−)-epicoccin G and (−)-rostratin A using a double C(sp³)−H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp³)−H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (−)-epicoccin G and to the more challenging (−)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (−)-epicoccin G and (−)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue.     

Synthesis of Amides and Esters by Palladium(0)-Catalyzed Carbonylative C(sp3)−H Activation

The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp³)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh₃ as the ligand, and leads to the amide rather than the previously reported indanone product.     

Observations of cavitation erosion pit formation

Previous investigations showed that a single cavitation bubble collapse can cause more than one erosion pit (Philipp & Lauterborn [1]). But our preliminary study showed just the opposite – that in some cases a single cavitation pit can result from more than one cavitation event. The present study shows deeper investigation of this phenomenon. An investigation of the erosion effects of ultrasonic cavitation on a thin aluminum foil was made. In the study we observed the formation of individual pits by means of high speed cameras (>1000 fps) and quantitatively evaluated the series of images by stereoscopy and the shape from shading method. This enabled the reconstruction of the time evolution of the pit shape. Results show how the foil is deformed several times before a hole is finally punctured. It was determined that larger single pits result from several impacts of shock waves on the same area, which means that they are merely special cases of pit clusters (pit clusters where pits overlap perfectly). Finally it was shown that a thin foil, which is subjected to cavitation, behaves as a membrane. It was concluded that the physics behind erosion depends significantly on the means of generating cavitation (acoustic, hydrodynamic, laser light) and the specimen characteristics (thin foil, massive specimen), which makes comparison of results of materials resistance to cavitation from different experimental set-ups questionable.Further development of the shape from shading method in the scope of cavitation erosion testing will enable better evaluation of cavitation erosion models.     

Use of a microelectromechanical mirror for adaptive optics in the human eye

Ophthalmic instrumentation equipped with adaptive optics offers the possibility of rapid and automated correction of the eye's optics for improving vision and for improving images of the retina. One factor that limits the widespread implementation of adaptive optics is the cost of the wave-front corrector, such as a deformable mirror. In addition, the large apertures of these elements require high pupil magnification, and hence the systems tend to be physically large. We present what are believed to be the first closed-loop results when a compact, low-cost, surface micromachined, microelectromechanical mirror is used in a vision adaptive-optics system. The correction performance of the mirror is shown to be comparable to that of a Xinetics mirror for a 4.6-mm pupil size. Furthermore, for a pupil diameter of 6.0-mm, the residual rms error is reduced from 0.36 to 0.12 microm and individual photoreceptors are resolved at a pupil eccentricity of 1 degrees from the fovea.     

Pierre Turq,an inspirational scientist in charge and at interfaces

Pierre Turq has made decisive contributions to the theory and to the multiscale simulation of charged systems, such as molten salts, electrolyte solutions and colloidal suspensions, in the bulk, at interfaces and under confinement. His research line focussed on dynamical properties and was characterised by constant efforts to connect his theoretical work to both experiments and practical applications. In this article, his colleagues and former students pay a tribute to his past and current research interests by illustrating some recent developments accomplished in his laboratory.