Alkali Metal Triphenyl- and Trihydridosilanides Stabilized by a Macrocyclic Polyamine Ligand

Potassium silanide [KSiH₃]_∞ contains 4.2 wt % of hydrogen and has been intensely studied as hydrogen storage material. The macrocyclic ligand Me₄TACD (1,4,7,10-tetramethyl-1,4,7,10-tetraaminocyclododecane, L ) stabilizes the full range of triphenylsilyl complexes [( L )MSiPh₃]_n (M=Li–Cs), which react with H₂ or PhSiH₃ to form molecular [( L )MSiH₃]_n that can be isolated in soluble form and fully characterized.     

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.     

A Cationic Zinc Hydride Cluster Stabilized by an N‐Heterocyclic Carbene: Synthesis,Reactivity, and Hydrosilylation Catalysis

The trinuclear cationic zinc hydride cluster [(IMes)₃Zn₃H₄(THF)](BPh₄)₂ ( 1 ) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH₂]₂ with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]²⁺. A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhS? SPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)₃SiH, giving silylformate as the main product.     

Method development and inter-laboratory comparison about the determination of titanium from titanium dioxide nanoparticles in tissues by inductively coupled plasma mass spectrometry

Nanosized titanium dioxide (TiO₂) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO₂. Total Ti levels were chosen to evaluate the presence and distribution of TiO₂ nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO₃) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO₂ nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO₂ dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 μg Ti/g tissue agreed well.

High performance parallel computing of flows in complex geometries

Efficient numerical tools taking advantage of the ever increasing power of high-performance computers, become key elements in the fields of energy supply and transportation, not only from a purely scientific point of view, but also at the design stage in industry. Indeed, flow phenomena that occur in or around the industrial applications such as gas turbines or aircraft are still not mastered. In fact, most Computational Fluid Dynamics (CFD) predictions produced today focus on reduced or simplified versions of the real systems and are usually solved with a steady state assumption. This article shows how recent developments of CFD codes and parallel computer architectures can help overcoming this barrier. With this new environment, new scientific and technological challenges can be addressed provided that thousands of computing cores are efficiently used in parallel. Strategies of modern flow solvers are discussed with particular emphases on mesh-partitioning, load balancing and communication. These concepts are used in two CFD codes developed by CERFACS: a multi-block structured code dedicated to aircrafts and turbo-machinery as well as an unstructured code for gas turbine flow predictions. Leading edge computations obtained with these high-end massively parallel CFD codes are illustrated and discussed in the context of aircrafts, turbo-machinery and gas turbine applications. Finally, future developments of CFD and high-end computers are proposed to provide leading edge tools and end applications with strong industrial implications at the design stage of the next generation of aircraft and gas turbines.     

Space averaging of vibration level differences measured in lightweight building structures

This paper examines space averaging methods applied to structural level differences measured in lightweight building structures (two beam junction and single plate and beam junction). The methods studied include the averaging assuming a constant input force, the averaging based on a constant vibration level across the source element, and the arithmetic averaging of level differences. Tests indicate that a fairly steady input force can be easily produced when using an impulsive source such as a hammer; the constant input force method is then appropriate and can be used to space average level differences (the two beam structure showing a standard deviation of 0.1 dB from the averaging based on levels normalised to the force). On the other hand, acceleration levels can exhibit significant variations with position due to the low mode count and modal overlap of some lightweight elements such as timber beams. Variations in the vibration level across the source element can then be responsible for large inaccuracies in the level difference calculated from the constant level assumption, the two beams’ results showing errors greater than 5 dB at several 1/3 octave band frequencies. The latter averaging method is then inappropriate and should not be used.     

The Effect of Temperature on Anisotropy Properties of an Aluminium Alloy

The temperature influence on the mechanical behaviour during plastic deformation of an AA5754-O aluminium alloy has been investigated by several experimental tests. First, monotonous tensile tests were carried out from room temperature up to 200°C with a classical tensile machine and with a less conventional testing apparatus involving the heating of the sample by Joule effect. With this second testing apparatus, the strain fields and tensile curves were obtained in function of temperature by means of a non-contacting optical 3D deformation measuring system. Moreover, shear tests were performed in the same temperature range. It is shown that the anisotropy coefficients are rather constant within this temperature range, with a relative variation less than 8%. For both tensile and shear tests, the stress levels are similar at the beginning of straining at room temperature and 150°C, except that the Portevin?CLe Chatelier (PLC) phenomenon disappears at elevated temperature, and then evolves differently. At 200°C, the stress level is clearly below whatever the deformation. In the framework of drawing process, the formability of this alloy at temperatures higher than 150°C seems to be improved.     

Numerical modeling of guided wave interaction with non-axisymmetric cracks in elastic cylinders

A three dimensional (3D) hybrid method combining the classical finite element (FE) method with the semi-analytical finite element (SAFE) technique is developed. This hybrid method is employed to study the interaction of guided waves with non-axisymmetric damages in cylinders. The near field surrounding the damage is analysed with the 3D FE method. The solution is expanded into sums of guided modes on both inlet and outlet cross-sections. Such eigenmode expansions enable separation into ingoing and outgoing waves, i.e., incident, reflected and transmitted waves. Using the SAFE method, elastic guided modes are then computed at the aforementioned cross-sections thus reducing the analysis to two dimensions (2D). The amplitudes of the incident modes are imposed, whereas those of the scattered modes are determined by solving the global system of the 3D hybrid FE-SAFE model. In this paper, a formula is proposed for the calculation of eigenforces and modal power flows from eigendisplacements and SAFE matrices. This has the advantage of simplifying the post-process of load eigenvectors in hybrid FE-SAFE methods. Results obtained for a vertical free-end cylinder are in good agreement with those published in the literature. Moreover, first results of the interaction of the fundamental compressional, flexural and torsional Pochhammer–Chree modes with non-axisymmetric vertical cracks are obtained and discussed. Then, the interactions of the fundamental compressional mode with oblique free-ends and cracks are briefly addressed. The power balance is shown to be satisfied with a good accuracy.     

Thermo-hydraulic characterization of a louvered fin and flat tube heat exchanger

In the present study, a whole heat exchanger with a hydraulic diameter of 2.3 mm is tested, which is a minichannel heat exchanger according to the Kandlikar classification. This is a louvered fin and flat tube heat exchanger currently used in car cooling systems, also known as radiator. A glycol-water mixture (60/40 in volume) circulates through the tubes at flows ranging from 100 to 7800 l/h and at a supply temperature of 90 °C. This fluid is cooled with ambient air at a temperature of 20 °C and at frontal air velocities varying between 0.5 and 7 m/s. The thermohydraulic performance of the heat exchanger is compared with the classical correlations given in the literature for the heat transfer and the friction factor calculation. On the glycol-water side the heat exchanger is characterized for Reynolds numbers from 30 to 8000. A first comparison is carried out with the correlations available in the literature with a purely predictive model by obtaining a predictive value with a systematic under prediction lower than 10%. In a second step a semi-empirical model is considered to identify the experimental heat transfer coefficients for this application.