Chiral Catalysts for Pd0-Catalyzed Enantioselective C−H Activation

In the past few decades, processes that involve transition-metal catalysis have represented a major part of the synthetic chemist′s toolbox. Recently, the interest has shifted from the well-established cross-coupling reactions to C−H bond functionalization, thus making it a current frontier of transition-metal-catalyzed reactions. Constant progress in this field has led to the discovery of enantioselective methods to generate and control various types of stereogenic elements, thereby demonstrating its high value to generate scalemic chiral molecules. The present review is dedicated to enantioselective Pd⁰-catalyzed C−H activation, which may be considered as an evolution of Pd⁰-catalyzed cross-couplings, with a focus on the different chiral ligands and catalysts that enable these transformations.     

Effect of high pressure on the reaction between bovine myofibrils and cathepsin D

This study deals with the effect of high pressure [50-500 MPa] and time of treatment [20-900 s] on the reaction between myofibrils and cathepsin D from bovine post mortem meat, using Surface Response Methodology. We shown that every high pressure treatment enhanced activity of cathepsin D as evaluated on haemoglobin as a substrate or on control meat myofibrils. We also put in evidence that cathepsin D could carry out the hydrolysis of high pressure treated myofibrils. At last we studied the action of pressurised cathepsin D on pressurised myofibrils, and proved that the hydrolysis was increasing up to 170 MPa and then decreased; above 300 MPa the activity was lower than with control cathepsin D and control myofibrils. Thus above 300 MPa recognition of natural substrate is affected by high pressure induced modifications. These results may help to explain why high pressure treatment of post rigor meat is not able to increase tenderness.     

Functional inequalities on manifolds with non-convex boundary

In this article, new curvature conditions are introduced to establish functional inequalities including gradient estimates, Harnack inequalities and transportation-cost inequalities on manifolds with non-convex boundary.     

Functional,hyperbranched polyesters via baylis–hillman polymerization

Hyperbranched polyesters are among the most common hyperbranched polymers. One of the interesting features of hyperbranched polyesters is that they contain unreacted hydroxyl and carboxylic acid groups at the linear and terminal structural units, which can be postmodified to adjust thermal, solubility, or mechanical properties, or to prepare core–shell type architectures. This article reports on the synthesis of a novel class of hyperbranched polyesters via an A₂ + B₃ type Baylis–Hillman polymerization of 2,6‐pyridinedicarboxaldehyde and trimethylolpropane triacrylate. Baylis–Hillman polymerization generates highly functional polyesters that contain not only unreacted aldehyde and/or acrylate groups at the linear and terminal structural units but also chemically orthogonal vinyl and hydroxyl groups along the polymer backbone. Using 3‐hydroxyquinuclidine as the catalyst, hyperbranched polymers with number‐average molecular weights up to 7500 g/mol and degrees of branching up to 0.81 were obtained. To demonstrate the versatility of these hyperbranched polyesters to act as platforms for further derivatization, the orthogonal postpolymerization modification of the hydroxyl, vinyl, and pyridine functional moieties with phenyl isocyanate, methyl‐3‐mercaptopropionate, and methyl iodide is presented. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

Optimization of the sensitivity and stability of the PRESAGE™ dosimeter using trihalomethane radical initiators

The aim of this study is to investigate the effect of trihalomethane radical initiators on the radiological properties, radiation dose sensitivity and post response photo-stability of the PRESAGE dosimeter. Different PRESAGE dosimeters containing 50 and 100 mM of iodoform (CHI₃), bromoform (CHBr₃) or chloroform (CHCl₃) radical initiators where fabricated and irradiated with 6 MV photons for a range of radiation doses from 0 to 30 Gy. A comparison between sensitivity and radiological properties of the PRESAGE dosimeters with the different radical initiators was carried out. Optical density changes of the dosimeters before and after irradiation were measured using a spectrophotometer. The incorporation of different radical initiators in the composition of the PRESAGE dosimeter resulted in variation of the radiation dose sensitivity and radiological properties of the dosimeters depending on the type and concentration of the radical initiator used, with iodoform showing the highest dose-response slope followed by bromoform and chloroform. However, at 100 mM iodoform, the effective atomic number was significantly higher than water (Z_eff=16). This enhancement in dose-response was found to be directly related to the carbon–halogen bond dissociation energy and to the radiological properties of each individual radical initiator used in this study. Furthermore, the post-response stability of the PRESAGE dosimeters over two weeks remained stable regardless of the trihalomethane radical initiator employed, with negligible change in the post-response stability and linearity of the PRESAGE dosimeters.     

Structure of Supramers Formed by the Amphiphile Biotin-CMG-DOPE

The synthetic function-spacer-lipid (FSL) amphiphile biotin-CMG-DOPE is widely used for delicate ligation of living cells with biotin residues under physiological conditions. Since this molecule has an “apolar-polar-hydrophobic” gemini structure, the supramolecular organization is expected to differ significantly from the classical micelle. Its organization is investigated with experimental methods and molecular dynamics simulations (MDS). Although the linear length of a single biotin-CMG-DOPE molecule is 9.5 nm, the size of the dominant supramer globule is only 14.6 nm. Investigations found that while the DOPE tails form a hydrophobic core, the polar CMG spacer folds back upon itself and predominantly places the biotin reside inside the globule or planar layer. MDS demonstrates that <10 % of biotin residues on the highly water dispersible globules and only 1 % of biotin residues in layer coatings are in an linear conformation and exposing biotin into the aqueous medium. This explains why in biotin-CMG-DOPE apolar biotin residues both in water dispersible globules and coatings on solid surfaces are still capable of interacting with streptavidin.     

Cosmic ray variations recorded by the CARPET facility on March 7, 2011

The CARPET cosmic ray detector was installed in 2006 in the Argentinean Andes at an altitude of 2550 m at the El Leoncito Astronomical Complex (CASLEO) in San Juan, Argentina (S31.8, W69.3; R _c = 9.659.65 GV). This instrument was developed at the Lebedev Physical Institute (LPI) in Russia as part of an international collaboration between the LPI, Brazil’s Mackenzie Center for Radioastronomy and Astrophysics (CRAAM), and the CASLEO. This work presents the results from analyzing variations in cosmic ray intensity recorded by the CARPET facility during the solar proton event of March 7, 2011. Also used in our analysis were the experimental data obtained by the GOES, FERMI, and ISS spacecraft during this solar event.     

Lightfront QED and Intense Field Physics

We briefly review the particular relevance of lightfront quantisation to QED in external fields modelling intense lasers.