Reactive organoallyl species generated from aryl halides and allene: allylation of alpha,beta-unsaturated aldehydes and cyclic ketones employing Pd/In transmetallation processes

Allylation of α,β-unsaturated aldehydes and cyclic ketones promoted by Pd/In transmetallation processes has been studied. The unsaturated aldehydes underwent regioselective 1,2-addition to afford secondary homoally alcohols. The reactions have been performed using Pd(OAc)2/PPh3 as catalytic system and metallic indium affording the products in good yields. The same transformation with unsaturated ketones proved to be less efficient, while saturated cyclic ketones delivered generally excellent yields in the presence of CuI. In these latter processes the presence of a distal heteroatom influences the reaction rate

On-sample water content measurement for a complete local monitoring in triaxial testing of unsaturated soils

To provide a complete local monitoring of the state of an unsaturated soil sample during triaxial testing, a local water content measurement device was adapted to a triaxial device comprising the measurement of local displacements (Hall effect transducers) and suction (High capacity transducer). Water content was locally monitored by means of a resistivity probe. The water content/resistivity calibration curves of an intact natural unsaturated loess from Northern France extracted by block sampling at two depths (1 and 3.3 m) were carefully determined, showing good accuracy and repeatability. The validity of two models giving the resistivity of unsaturated soils with respect to their water content was examined

Development of a Computer Vision-Based Three-Dimensional Reconstruction Method for Volume-Change Measurement of Unsaturated Soils during Triaxial Testing

Problems associated with unsaturated soils are ubiquitous in the U.S., where expansive and collapsible soils are some of the most widely distributed and costly geologic hazards. Solving these widespread geohazards requires a fundamental understanding of the constitutive behavior of unsaturated soils. In the past six decades, the suction-controlled triaxial test has been established as a standard approach to characterizing constitutive behavior for unsaturated soils. However, this type of test requires costly test equipment and time-consuming testing processes. To overcome these limitations, a photogrammetry-based method has been developed recently to measure the global and localized volume-changes of unsaturated soils during triaxial test. However, this method relies on software to detect coded targets, which often requires tedious manual correction of incorrectly coded target detection information. To address the limitation of the photogrammetry-based method, this study developed a photogrammetric computer vision-based approach for automatic target recognition and 3D reconstruction for volume-changes measurement of unsaturated soils in triaxial tests. Deep learning method was used to improve the accuracy and efficiency of coded target recognition. A photogrammetric computer vision method and ray tracing technique were then developed and validated to reconstruct the three-dimensional models of soil specimen

A 1-D modelling of streaming potential dependence on water content during drainage experiment in sand

The understanding of electrokinetics for unsaturated conditions is crucial for numerous of geophysical data interpretation. Nevertheless, the behaviour of the streaming potential coefficient C as a function of the water saturation Sw is still discussed. We propose here to model both the Richards' equation for hydrodynamics and the Poisson's equation for electrical potential for unsaturated conditions using 1-D finite element method. The equations are first presented and the numerical scheme is then detailed for the Poisson's equation. Then, computed streaming potentials (SPs) are compared to recently published SP measurements carried out during drainage experiment in a sand column. We show that the apparent measurement of DV / DP for the dipoles can provide the SP coefficient in these conditions. Two tests have been performed using existing models for the SP coefficient and a third one using a new relation. The results show that existing models of unsaturated SP coefficients C(Sw) provide poor results in terms of SP magnitude and behaviour. We demonstrate that the unsaturated SP coefficient can be until one order of magnitude larger than Csat, its value at saturation. We finally prove that the SP coefficient follows a non-monotonous behaviour with respect to water saturation. Key words: Electrical properties; Electromagnetic theory; Hydrogeophysics; Hydrology; Permeability and porosity; electrokinetic; streaming potential; self-potential; water content; water saturation; unsaturated condition; finite element modelin

Lateral phase separation in mixtures of lipids and cholesterol

In an effort to understand "rafts" in biological membranes, we propose phenomenological models for saturated and unsaturated lipid mixtures, and lipid-cholesterol mixtures. We consider simple couplings between the local composition and internal membrane structure, and their influence on transitions between liquid and gel membrane phases. Assuming that the gel transition temperature of the saturated lipid is shifted by the presence of the unsaturated lipid, and that cholesterol acts as an external field on the chain melting transition, a variety of phase diagrams are obtained. The phase diagrams for binary mixtures of saturated/unsaturated lipids and lipid/cholesterol are in semi-quantitative agreement with the experiments. Our results also apply to regions in the ternary phase diagram of lipid/lipid/cholesterol systems

Modelling plasticity of unsaturated soils in a thermodynamically consistent framework

Constitutive equations of unsaturated soils are often derived in a thermodynamically consistent framework through the use a unique 'effective' interstitial pressure. This later is naturally chosen as the space averaged interstitial pressure. However, experimental observations have revealed that two stress state variables were needed to describe the stress-strain-strength behaviour of unsaturated soils. The thermodynamics analysis presented here shows that the most general approach to the behaviour of unsaturated soils actually requires three stress state variables: the suction, which is required to describe the retention properties of the soil and two effective stresses, which are required to describe the soil deformation at water saturation held constant. Actually, it is shown that a simple assumption related to internal deformation leads to the need of a unique effective stress to formulate the stress-strain constitutive equation describing the soil deformation. An elastoplastic framework is then presented and it is finally shown that the Barcelona Basic Model, a commonly accepted model for unsaturated soils, as well as all models deriving from it, appear as special extreme cases of the thermodynamic framework proposed here

Growth inhibition and morphologic changes of HeLa cells exposed to unsaturated fatty acid fraction from the liver of x-ray irradiated rabbits (OX)

Biological effect of the unsaturated fatty acid fraction from the X-ray irradiated rabbit liver (OX) on HeLa cells has been observed in vitro comparing with the effect displayed on the same strain cells by the unsaturated fatty acid fraction from the non-irradiated rabbits, which is extracted by the same method as in OX, The observations have proven that OX is a powerful cytotoxin in a concentration of 0.05-0.025 per cent and induces a severe cell degeneration and cell death, resulting in a marked arrest in the growth of the cells. The similar effect has been observed by unsaturated fatty acid fraction from the nonirradiated rabbits, but the effect was much less comparing to that of OX. Possible mechanism of the cell damage by OX has been discussed.</p