Toward a synthetically useful stereoselective C-H amination of hydrocarbons

Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (<=3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions.     

Equivalent moduli of continuity, Bloch’s theorem for pluriharmonic mappings in mathbb{B}{kern-8pt}mathbb{B}^{boldsymbol n}

In this paper, we first establish a Schwarz?CPick type theorem for pluriharmonic mappings and then we apply it to discuss the equivalent norms on Lipschitz-type spaces. Finally, we obtain several Landau??s and Bloch??s type theorems for pluriharmonic mappings.     

On the enhancement of diffusion by chaos, escape rates and stochastic instability

We consider stochastic perturbations of expanding maps of the interval where the noise can project the trajectory outside the interval. We estimate the escape rate as a function of the amplitude of the noise and compare it with the purely diffusive case. This is done under a technical hypothesis which corresponds to stability of the absolutely continuous invariant measure against small perturbations of the map. We also discuss in detail a case of instability and show how stability can be recovered by considering another invariant measure.

     

A calorimetric comparative study of hydrogenated and deuterated diacetylene 2,4 hexadiynylene bis(p-toluenesulfonate): Phase diagrams and polymerization

Microcalorimetry was used to study the thermal polymerization and the structural instabilities in hydrogenated (pTS-H) and deuterated (pTS-D) diacetylene 2,4-hexadiynylene bis(p-toluenesulfonate). In the induction period, the polymerization reaction proceeds about seven times faster in pTS-D than in pTS-H. Whereas the phase transitions of pure pTS-H and pTS-D monomer crystals and of pure pTS-H and pTS-D polymer crystals are very similar, the situation is completely different for mixed monomer-polymer crystals of pTS-H and pTS-D. The results are interpreted by studying comparative influence of the chain lengths for pTS-H and pTS-D oligomers. A comparison is made between these results and previous experimental results obtained from dielectric measurements, UV-spectroscopy, X-ray, and elastic neutron scattering. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 789–798, 1997     

Polynuclear SmIII Polyamidoamine‐Based Dendrimer: A Single Probe for Combined Visible and Near‐Infrared Live‐Cell Imaging

We report herein the synthesis of a luminescent polynuclear dendritic structure (Sm^III‐G3P‐2,3Nap) in which eight Sm^III ions are sensitized by thirty‐two 2,3‐naphthalimide chromophores. Upon a single excitation wavelength, the dendrimer complex exhibits two types of emission in the visible and in the near‐infrared (NIR) ranges. Sm^III‐G3P‐2,3Nap was non‐cytotoxic after 24 h of incubation and up to 2.5 μM . The ability of the Sm^III‐based probe to be taken up by cells was confirmed by confocal microscopy. Epifluorescence microscopy validated Sm^III‐G3P‐2,3Nap as a versatile probe, capable of performing interchangeably in the visible or NIR for live‐cell imaging. As both emissions are obtained from a single complex, the cytotoxicity and biodistribution are inherently the same. The possibility for discriminating the sharp Sm^III signals from autofluorescence in two spectral ranges increases the reliability of analysis and reduces the probability of artifacts and instrumental errors.     

On nonconservativeness of Eringen’s nonlocal elasticity in beam mechanics: correction from a discrete-based approach

In this paper, the self-adjointness of Eringen’s nonlocal elasticity is investigated based on simple one-dimensional beam models. It is shown that Eringen’s model may be nonself-adjoint and that it can result in an unexpected stiffening effect for a cantilever’s fundamental vibration frequency with respect to increasing Eringen’s small length scale coefficient. This is clearly inconsistent with the softening results of all other boundary conditions as well as the higher vibration modes of a cantilever beam. By using a (discrete) microstructured beam model, we demonstrate that the vibration frequencies obtained decrease with respect to an increase in the small length scale parameter. Furthermore, the microstructured beam model is consistently approximated by Eringen’s nonlocal model for an equivalent set of beam equations in conjunction with variationally based boundary conditions (conservative elastic model). An equivalence principle is shown between the Hamiltonian of the microstructured system and the one of the nonlocal continuous beam system. We then offer a remedy for the special case of the cantilever beam by tweaking the boundary condition for the bending moment of a free end based on the microstructured model.