Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation.     

Narrow-line phase-locked quantum cascade laser in the 9.2 microm range

We report the operation of a 50 mW continuous-wave quantum cascade laser (QCL) in the 9.2 microm range, phase locked to a single-mode CO(2) laser with a tunable frequency offset. The wide free-running emission spectrum of the QCL (3-5 MHz) is strongly narrowed down to the kilohertz range, making it suitable for high-resolution molecular spectroscopy.     

A well-balanced and asymptotic-preserving scheme for the one-dimensional linear Dirac equation

The numerical approximation of one-dimensional relativistic Dirac wave equations is considered within the recent framework consisting in deriving local scattering matrices at each interface of the uniform Cartesian computational grid. For a Courant number equal to unity, it is rigorously shown that such a discretization preserves exactly the \(L^2\) norm despite being explicit in time. This construction is well-suited for particles for which the reference velocity is of the order of \(c\), the speed of light. Moreover, when \(c\) diverges, that is to say, for slow particles (the characteristic scale of the motion is non-relativistic), Dirac equations are naturally written so as to let a “diffusive limit” emerge numerically, like for discrete 2-velocity kinetic models. It is shown that an asymptotic-preserving scheme can be deduced from the aforementioned well-balanced one, with the following properties: it yields unconditionally a classical Schrödinger equation for free particles, but it handles the more intricate case with an external potential only conditionally (the grid should be such that \(c \Delta x\rightarrow 0\)). Such a stringent restriction on the computational grid can be circumvented easily in order to derive a seemingly original Schrödinger scheme still containing tiny relativistic features. Numerical tests (on both linear and nonlinear equations) are displayed.     

Nanotextured multicrystalline Al‐BSF solar cells reaching 18% conversion efficiency using industrially viable solar cell processes

We report recent achievements in adapting industrially used solar cell processes on nanotextured surfaces. Nanostructures were etched into c‐Si surfaces by dry exothermic plasma‐less reaction of F species with Si in atmospheric pressure conditions and then modified using a short post‐etching process. Nanotextured multicrystalline wafers are used to prepare Al‐BSF solar cells using industrially feasible solar cell proc‐ essing steps. In comparison to the reference acidic textured solar cells, the nanostructured cells showed gain in short circuit current (J_sc) of up to 0.8 mA/cm² and absolute gain in conversion efficiency of up to 0.3%. The best nanotextured solar cell was independently certified to reach the conversion efficiency of 18.0%. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold

Oxidative addition plays a major role in transition‐metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl₃, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative ³¹P and ²⁹Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si? Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si? Si) bonds to gold and open promising perspectives for the development of new gold‐catalyzed redox transformations.     

Heart Regeneration: Opportunities and Challenges for Drug Discovery with Novel Chemical and Therapeutic Methods or Agents

Following a heart attack, more than a billion cardiac muscle cells (cardiomyocytes) can be killed, leading to heart failure and sudden death. Much research in this area is now focused on the regeneration of heart tissue through differentiation of stem cells, proliferation of existing cardiomyocytes and cardiac progenitor cells, and reprogramming of fibroblasts into cardiomyocytes. Different chemical modalities (i.e. methods or agents), ranging from small molecules and RNA approaches (including both microRNA and anti‐microRNA) to modified peptides and proteins, are showing potential to meet this medical need. In this Review, we outline the recent advances in these areas and describe both the modality and progress, including novel screening strategies to identify hits, and the upcoming challenges and opportunities to develop these hits into pharmaceuticals, at which chemistry plays a key role.     

Predicting New Ugi–Smiles Couplings: A Combined Experimental and Theoretical Study

Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles.     

On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2

The electronic ground and excited states of the coordinatively unsaturated complex Ni(η¹‐N₂)₂, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η¹‐N₂)₂ with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η¹‐N₂)(η²‐N₂) and Ni(η²‐N₂)₂, with one and two side‐on coordinated dinitrogen ligands, respectively.     

Functionalization of a Ruthenium–Diacetylide Organometallic Complex as a Next‐Generation Push–Pull Chromophore

The design and preparation of an asymmetric ruthenium–diacetylide organometallic complex was successfully achieved to provide an original donor–π–[M]–π–acceptor architecture, in which [M] corresponds to the [Ru(dppe)₂] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge‐transfer processes occurring upon photoexcitation of the push–pull metal–dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push–pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye‐sensitized solar cell devices, showed a good spectral response with a broad incident photon‐to‐current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications.