A route to annulated indoles via a palladium-catalyzed tandem alkylation/direct arylation reaction

A norbornene-mediated palladium-catalyzed tandem alkylation/C-H functionalization sequence is described, in which an alkyl-aryl bond and a heteroaryl-aryl bond are formed in one pot. A variety of highly substituted six- and seven-membered ring annulated indoles were synthesized in good yields from bromoalkyl indoles and aryl iodides.     

The diazo route to diazonamide A: studies on the tyrosine-derived fragment

Various approaches to the tyrosine-derived fragment of the marine secondary metabolite diazonamide A are described. Initial efforts were focused on the originally proposed structure of the natural product, and a feasibility study established that a model 4-aryltryptamine could be readily prepared. Protected 4-bromotryptamine underwent Pd0-catalyzed coupling with the boronic acid derived from 2-bromophenyl allyl ether by Claisen rearrangement, O-methylation and lithiation-boration. The resulting biaryl was elaborated into an alpha-diazo-beta-ketoester, dirhodium(II)-catalyzed reaction of which with N-Z-valinamide gave the desired tryptamine-oxazole following cyclodehydration of the intermediate ketoamide. A potential precursor to the benzofuran ring of the original structure of diazonamide A was prepared in eight steps from N-Z-tyrosine tert-butyl ester. Iodination, O-protection and Stille coupling gave the cinnamyl alcohol 25, converted via the bromide into the allyl aryl ether 27. Subsequent Claisen rearrangement and oxidative cleavage of the alkene gave the lactol 29, converted into the desired benzofuranone 31. The revision in the structure of diazonamide A to 2 resulted in the targeting of an alternative tyrosine-derived model benzofuranone 41 synthesized in four steps from N-Z-tyrosine methyl ester 36 by a route involving Claisen rearrangement of cinnamyl ether 37. Poor yields in this sequence prompted an investigation into the intramolecular Heck reaction as a route to benzofuranone 50. Coupling of 3-iodotyrosine 44 with 2-phenylbutenoic acid 48 gave ester 49 that readily underwent intramolecular Heck reaction to give benzofuranone 50, albeit with poor stereocontrol.     

Deposition and Characterization of Metastable Cu3N Layers for Applications in Optical Data Storage

 Cu₃N films for optical data storage were deposited on Si(100) wafers and 0.6 mm thick polycarbonate DVD base material discs at a temperature of 50 °C by reactive magnetron sputtering. A copper target was sputtered in rf mode in a nitrogen plasma. For basic investigations concerning the composition and structure of Cu₃N, Si wafers were used as substrate material. To study the suitability of Cu₃N as an optical data storage medium under technical conditions, Cu₃N/Al bilayers were deposited on polycarbonate discs. The composition and structure of the films were investigated by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The decomposition of Cu₃N into metallic copper and nitrogen was induced and characterized with a dynamic tester consisting of an optical microscope with an integrated high power laser diode. The change in reflectivity induced by the laser pulses was measured by a high sensitivity photo detector. Optimized Cu₃N films could be decomposed into metallic copper at pulse lengths of 200 ns. The reflectivity change from 3.2% to 33.2% for completely transformed areas and to 12% for single bits as well as the maximum write data rate of 3.3 Mbit/s demonstrated the suitability of Cu₃N for write once optical data storage. Especially the carrier to noise ratio of 41 dB shows an increase of a factor of 3 for this novel material as compared to conventional optical data storage media.     

Experimental investigation of turbulence modulation in particle-laden coaxial jets by Phase Doppler Anemometry

The effect of solid particles on the flow characteristics of axisymmetric turbulent coaxial jets for two flow conditions was studied. Simultaneous measurements of size and velocity distributions of continuous and dispersed phases in a two-phase flow are presented using a Phase Doppler Anemometry (PDA) technique. Spherical glass particles with a particle diameter range from 102 to 212 μm were used in this two-phase flow, the experimental results indicate a significant influence of the solid particles and the Re on the flow characteristics. The data show that the gas phase has lower mean velocity in the near-injector region and a higher mean velocity at the developed region. Near the injector at low Reynolds number (Re = 2839) the presence of the particles dampens the gas-phase turbulence, while at higher Reynolds number (Re = 11 893) the gas-phase turbulence and the velocity fluctuation of particle-laden jets are increased. The particle velocity at higher Reynolds number (Re = 11 893) and is lower at lower Reynolds number (Re = 2839). The slip velocity between particles and gas phase existed over the flow domain was examined. More importantly, the present experiment results suggest that, consideration of the gas characteristic length scales is insufficient to predict gas-phase turbulence modulation in gas-particle flows.     

A method for 13C‐labeling of metabolic carbohydrates within French bean leaves (Phaseolus vulgaris L.) for decomposition studies in soils

The molecular composition of plant residues is suspected to largely govern the fate of their constitutive carbon (C) in soils. Labile compounds, such as metabolic carbohydrates, are affected differently from recalcitrant and structural compounds by soil‐C stabilisation mechanisms. Producing ¹³C‐enriched plant residues with specifically labeled fractions would help us to investigate the fate in soils of the constitutive C of these compounds. The objective of the present research was to test ¹³C pulse chase labeling as a method for specifically enriching the metabolic carbohydrate components of plant residues, i.e. soluble sugars and starch. Bean plants were exposed to a ¹³CO₂‐enriched atmosphere for 0.5, 1, 2, 3 and 21 h. The major soluble sugars were then determined on water‐soluble extracts, and starch on HCl‐hydrolysable extracts. The results show a quick differential labeling between water‐soluble and water‐insoluble compounds. For both groups, ¹³C‐labeling increased linearly with time. The difference in δ¹³C signature between water‐soluble and insoluble fractions was 7‰ after 0.5 h and 70‰ after 21 h. However, this clear isotopic contrast masked a substantial labeling variability within each fraction. By contrast, metabolic carbohydrates on the one hand (i.e. soluble sugars + starch) and other fractions (essentially cell wall components) on the other hand displayed quite homogeneous signatures within fractions, and a significant difference in labeling between fractions: δ¹³C = 414 ± 3.7‰ and 56 ± 5.5‰, respectively. Thus, the technique generates labeled plant residues displaying contrasting ¹³C‐isotopic signatures between metabolic carbohydrates and other compounds, with homogenous signatures within each group. Metabolic carbohydrates being labile compounds, our findings suggest that the technique is particularly appropriate for investigating the effect of compound lability on the long‐term storage of their constitutive C in soils. Copyright © 2009 John Wiley & Sons, Ltd.     

Experimental analysis of the influence of damping on the resonance behavior of a spherical pendulum

This study describes the experimental and numerical dynamic analysis of a kinematically excited spherical pendulum. The stability of the response in the vertical plane was analyzed in the theoretically predicted auto-parametric resonance domain. Three different types of the resonance domain were investigated the properties of which depended significantly on the dynamic parameters of the pendulum and the excitation amplitude. A mathematical model was used to represent the nonlinear characteristics of the pendulum, which includes the asymmetrical damping. A special frame was developed to carry out the experiments, which contained the pendulum supported by the Cardan joint and two magnetic units attached to the supporting axes of rotation, and this was able to reproduce linear viscous damping for both of the principal response components. The stability analysis of the system was compared with the numerical solution of the governing equations and experimental observation. The most significant practical outcomes for designers are also summarized.     

Heat transfer from a line source located in the periodic laminar near wake of a circular cylinder

This experimental study is devoted to the diffusion of a passive scalar downstream a line source located in a Bénard–von Kármán street. Measurements of velocity and temperature have been performed using LDA and cold wire thermometer with a phase reference. Information on the initial evolution of mean, fluctuating velocity and temperature and associated shear-stresses and heat fluxes fields are presented for two locations of the source: ( and 1). The results show that the velocity field in the wake is strongly related to the geometric structure of vortices while the temperature field is controlled by both the time scale of rotation of the vortices and the location of the heated fluid within the vortex street.     

Fractal First-Order Partial Differential Equations

The present paper is concerned with semi-linear partial differential equations involving a particular pseudo-differential operator. It investigates both fractal conservation laws and non-local Hamilton–Jacobi equations. The idea is to combine an integral representation of the operator and Duhamel's formula to prove, on the one hand, the key a priori estimates for the scalar conservation law and the Hamilton–Jacobi equation and, on the other hand, the smoothing effect of the operator. As far as Hamilton–Jacobi equations are concerned, a non-local vanishing viscosity method is used to construct a (viscosity) solution when existence of regular solutions fails, and a rate of convergence is provided. Turning to conservation laws, global-in-time existence and uniqueness are established. We also show that our formula allows us to obtain entropy inequalities for the non-local conservation law, and thus to prove the convergence of the solution, as the non-local term vanishes, toward the entropy solution of the pure conservation law.     

Dilational rheology of an air–water interface functionalized by biomolecules: the role of surface diffusion

As an attempt to develop a sensitive device for biomolecule detection, a micromechanical methodology based on the rheological change of an air–water interface is put forward (Berthier and Davoust, CEA/CNRS patent, PCT International Application WO 2003/080209 A3, 2003). Capillary waves induced from the vertical electrodynamic vibration of a brimful cylindrical tank filled with water stand as a good way to identify dilational elasticity and viscosity of an aging interface. Before, we were interested of the fact that complex wave number and the frequency of waves are obtained through an optical technique, which allows us to accurately recognize the whole interface geometry. These two parameters, a modeling based on a dispersion relation (Lucassen-Reynders and Lucassen, Adv Colloid Interface Sci, 2:347, 1969) and the surface mass transport equation, are jointly used to identify the surface diffusivity and the dilational rheology of the interface for a nonsoluble biochemical surfactant. Preliminary results obtained from a water surface functionalized by DNA, thanks to a lipidic monolayer, demonstrate the capabilities of the proposed methodology. The sensitivity of dilational rheology and the surface diffusivity on DNA adsorption on lipids is made evident.This paper was presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005.     

Kinematostatic modeling of compliant parallel mechanisms

The benefits of compliant mechanisms in terms of precision are not easy to exploit because of the limitations of the existing kinematic models used to analyze them. In practice, compliant mechanisms are more sensitive to external wrenches than conventional mechanisms. In this paper, based on the kinematic constraints and the static equilibrium between the joint coordinates and the external wrenches, a general kinematostatic model of compliant parallel mechanisms is presented. Then, this model is differentiated to provide a quasi-static model that makes it possible to calculate the variation of the pose as a linear function of the motion of the actuators and the variation of the external loads through two new matrices: the quasi-static Jacobian matrix and the Cartesian compliance matrix that give a simple and meaningful formulation of the model of the mechanism.