Tuning the Regioselective Functionalization of Trifluoromethylated Dienes via Lanthanum-Mediated Single C−F Bond Activation

The development of new fluorine-containing building blocks and their efficient synthetic access is currently a challenging research field. Herein, the highly regio- and stereoselective addition of a large range of aldehydes onto trifluoromethylated benzofulvenes was achieved using a simple La/I₂/DIBAL-Cl system via a selective C−F bond activation process. This versatile methodology provided homodienyl alcohols bearing a terminal CF₂-alkene with potential further applications, as shown by the dehydration to the first benzofulvenes carrying a difluorovinyl group. In addition, for certain electron-poor aldehydes, unprecedented ipso substitution of the CF₃ group in a diene was observed, which, according to DFT studies, is related to the presence of the large, Lewis-acidic lanthanum metal.     

Evaluation of antileishmanial, cytotoxic and antioxidant activities of essential oils extracted from plants issued from the leishmaniasis-endemic region of Sned (Tunisia)

In this study, we tested 10 essential oils (EOs) extracted from 10 plants issued from Sned region (Tunisia) to evaluate both their leishmanicidal effects against Leishmania major and L. infantum, and their cytotoxicity against murine macrophage cell line RAW 264.7 (ATCC, TIB-71). The antioxidant activity was also monitored by the DDPH method, while the chemical composition of active EO was assessed by GC-MS analysis. The results showed that the EOs obtained from Thymus hirtus sp. algeriensis (rich on monoterpenoids, especially linalool at 17.62% and camphor at 13.82%) is significantly active against both L. major and L. infantum, whereas Ruta chalepensis EO (rich on 2-undecanone at 84.28%) is only active against L. infantum. Both oil extracts showed low cytotoxicity towards murine macrophages. The characteristic ratios (IC?? Raw264.7 cells/IC?? L. infantum and IC?? Raw264.7 cells/IC?? L. major) were, respectively, 2.7 and 1.57 for T. hirtus sp. algeriensis, and 1.34 and 0.19 for R. chalepensis. However, when measuring the antioxidant effects (DDPH method), the two latter EOs presented a moderate 2,2-diphenyl-2-picrylhydrazyl hydrate scavenging effects compared to EOs from Eucaliptus globulus, Pinus halepensis, Pituranthos tortuosus, Rosmarinus officinalis, Tetraclinis articulata or to BHT.     

Classification of Fe‐bearing species from K‐edge XANES data using two‐parameter correlation plots

Solid iron compounds are extremely common in the environment as well as in meteorites and comets. Fe K‐edge XANES (X‐ray absorption near‐edge structure) measurements can be carried out quickly, theoretically allowing one to categorize many areas within a sample or set of samples in a short time. However, interpretation of such data is not straightforward unless one has the appropriate reference spectra, hence a way of classifying an unknown spectrum to a family group (trivalent, divalent, oxide, silicate etc.) is required. Methods of abstracting Fe XANES spectra to produce pairs of variables which, when plotted, cluster in distinct regions depending on the family are presented. For instance, divalent minerals fall in a different region than trivalent minerals, and sulfides in a different region than oxides.     

Elongated Bacterial Pili as a Versatile Alignment Medium for NMR Spectroscopy

In NMR spectroscopy, residual dipolar couplings (RDCs) have emerged as one of the most exquisite probes of biological structure and dynamics. The measurement of RDCs relies on the partial alignment of the molecule of interest, for example by using a liquid crystal as a solvent. Here, we establish bacterial type 1 pili as an alternative liquid-crystalline alignment medium for the measurement of RDCs. To achieve alignment at pilus concentrations that allow for efficient NMR sample preparation, we elongated wild-type pili by recombinant overproduction of the main structural pilus subunit. Building on the extraordinary stability of type 1 pili against spontaneous dissociation and unfolding, we show that the medium is compatible with challenging experimental conditions such as high temperature, the presence of detergents, organic solvents or very acidic pH, setting it apart from most established alignment media. Using human ubiquitin, HIV-1 TAR RNA and camphor as spectroscopic probes, we demonstrate the applicability of the medium for the determination of RDCs of proteins, nucleic acids and small molecules. Our results show that type 1 pili represent a very useful alternative to existing alignment media and may readily assist the characterization of molecular structure and dynamics by NMR.     

Crystal structures and physico-chemical properties of Zn(II) and Co(II) tetraaqua(3-nitro-4-hydroxybenzoato) complexes: Their anticonvulsant activities as well as related (5-nitrosalicylato)–metal complexes

Purposes of these studies were to synthesize Zn(II) and Co(II) complexes of 3-nitro-4-hydroxybenzoic acid, determine their structures through X-ray crystallography, and obtain their anticonvulsant activities. Thermogravimetric, differential scanning calorimetry, impedance of aqueous solutions and magnetic properties analyses were also determined. Anticonvulsant and related activities of these complexes as well as Zn(II), Co(II), Ni(II) and Mg(II) (5-nitrosalicylato) complexes were determined by the National Institutes of Health, Antiepileptic Development Program. Results of these analyses are presented to document unique bonding features and physical properties of these compounds and their anticonvulsant activities. It is concluded that these compounds have chemical and physical properties that can be used to account for their anticonvulsant activities.     

Effect of Efflorescence Formation on Drying Kinetics of Porous Media

We study experimentally the evaporation of an aqueous NaCl solution with efflorescence formation in hydrophilic or hydrophobic two-dimensional model porous media. The efflorescence formation only marginally affects the invasion patterns but greatly modifies the drying kinetics compared to pure water. Two mechanisms are identified for explaining the impact of efflorescence formation on drying kinetics. It is shown that the efflorescence contributes to increase the evaporation rate compared to drying with pure water, a surprising result since the water activity is reduced in the presence of dissolved salt. This effect is explained by the efflorescence liquid capillary pumping effect associated with the porous nature of the efflorescence. Then, we identify a second phase where the efflorescence dries out and acts as a vapour diffusion barrier, leading to a dramatic reduction of evaporation rate.     

A theoretical study of radiation between two concentric spheres using a modified discrete ordinates method associated with Legendre transform

A modified discrete ordinates method (DOM) is used in spherical participating media. The radiative intensity is broken up into two components. One component is traced back to the enclosure's source. It is called direct intensity. The other component is rather traced back to the contribution of the medium itself. It is called diffuse intensity. Thus, the radiative transfer equation (RTE) is transformed into two simultaneous equations: a direct RTE and a diffuse RTE. The direct RTE is solved analytically. The diffuse RTE is solved numerically using the DOM. The streaming angular derivative term appearing in spherical geometry is modeled by making use of the Finite Legendre Transform. We study a pure radiation transfer problem between two concentric spheres. The medium is assumed to be gray and isotropically scattering. The limiting spheres are considered to be opaque, gray, diffusely emitting and diffusely reflecting with uniform emissivity over each surface. The obtained results are compared with available cases reported in the literature. In particular, relative importance of the direct radiation in optically thin media is studied.