Point defect dynamics and evolution of chemical reactions in alanates by anelastic spectroscopy

We report the first measurements of elastic modulus and energy dissipation in Ti-doped and undoped sodium aluminum hydride. It is shown that the chemical reactions that occur by varying the sample temperatures or by aging most sensitively affect the elastic constants, such that the modulus variations allow the time and temperature evolution of decomposition to be monitored. After a well-defined thermal treatment at 436 K, a thermally activated relaxation process appears at 70 K in the kilohertz range, denoting the existence of a new species, likely involving hydrogen, having a very high mobility, that is, 10(3) jumps/s at the peak temperature corresponding to a relaxation rate of about 10(11) s(-1) at room temperature. The activation energy of the process is 0.126 eV and the preexponential factor 7 x 10(-14) s, which is typical of point defect relaxation. The peak is very broad with respect to a single Debye process, indicating strong interaction or/and multiple jumping type of the mobile entity. The present data suggest that the models aiming at interpreting the decomposition reactions and kinetics should take into account the indicated point-defect dynamics and stoichiometry defects.     

Chemistry of iron carbonyl anions: Selective reduction of nitroarenes and α, β-unsaturated carbonyl compounds,and reductive dehalogenation of organic halides by (C2H5)4N+ HFe3(CO)11−

The tetraethylammonium undecacarbonylhydridotriferrate [(C₂H₅)₄N⁺ HFe₃(CO)₁₁^?] (I): which can be easily prepared in a two-step sequence from iron pentacarbonyl, triethylamine and tetraethylammonium chloride, selectively reduces nitroarenes to amines and α, β-unsaturated carbonyl compounds to the corresponding saturated compounds both in good yield. I reacts with some organic halides to give dehalogenated products.     

New liquid chromatography/electron ionization mass spectrometry methods in water analysis

A method to extract and analyze organic compounds from water is presented. A solid phase micro-trap (micro-SPE) directly connected to the micro-analytical column is used. Sensibility and specificity needed for trace analysis are guaranteed by mass spectrometric electron ionization (EI) detection. A new micro-HPLC/EI-MS interface called Capillary-EI (Cap-EI) is described. The ultimate evolution of this interface is also presented: in this extremely simplified interface the analytes are nebulized, vaporized and ionized in the small volume of the ion source. This interface, called Direct-EI, exploits nano- and micro-HPLC columns with a mobile phase flow rates ranging from 0.3 to 1.5 microL/min. Contemporary use of micro SPE, Cap-EI or Direct-EI gives us a powerful technique to identify and quantify organic pollutants at part per billion level (ppb).     

Chemo- and Regioselective Anionic Fries Rearrangement Promoted by Lithium Amides under Aerobic Conditions in Sustainable Reaction Media

A straightforward and efficient protocol to promote the metalation/anionic Fries rearrangements of O-aryl carbamates, using for the first time a lithium amide as metalating agent under aerobic/ambient-friendly reaction conditions, is reported. This approach enables the sustainable preparation of salicylamide derivatives with high levels of chemoselectivity within ultrafast reaction times, working at room temperature in the presence of air/moisture, and using environmentally responsible cyclopentyl methyl ether as a solvent. Furthermore, the regioselective manipulation of O-2-tolyl carbamates has been accomplished using interchangeably alkyllithiums or lithium amides, with an unexpected beneficial contribution from the employment of biorenewable protic eutectic mixtures as non-innocent reaction media.     

Multiple Timescales Analysis for 1:2 and 1:3 Resonant Hopf Bifurcations

The postcritical behavior of a generaln-dimensional system around a resonant double Hopf bifurcation isanalyzed. Both cases in which the critical eigenvalues are in ratios of1:2 and 1:3 are investigated. The Multiple Scale Method is employedto derive the bifurcation equations systematically in terms of thederivatives of the original vector field evaluated at the criticalstate. Expansions of the n-dimensional vector of state variables andof a three-dimensional vector of control parameters are performed interms of a unique perturbation parameter ε, of the order ofthe amplitude of motion. However, while resonant terms only appear atthe ε³-order in the 1:3 case, they already arise at theε²-order in the 1:2 case. Thus, by truncating theanalysis at the ε³-order in both cases, first orsecond-order bifurcation equations are respectively drawn, the latterrequiring resort to the reconstitution principle. A two-degrees-of-freedom system undergoing resonant double Hopf bifurcations isstudied. The complete postcritical scenario is analyzed in terms of thethree control parameters and the asymptotic results are compared withexact numerical integrations for both resonances. Branches of periodicas well as periodically modulated solutions are found and theirstability analyzed.     

Flexural-torsional bifurcations of a cantilever beam under potential and circulatory forces II. Post-critical analysis

The post-critical behavior of a cantilever beam with rectangular cross-section, under simultaneous action of conservative and non-conservative loads, is analyzed. An internally constrained Cosserat rod model is adopted to describe the dynamics of the beam in finite displacement regime. The bifurcation equations for simple buckling (divergence), simple flutter (Hopf) and double-zero (Takens-Bogdanova-Arnold) bifurcations are derived by means of the multiple time scales method. Due to the nilpotent eigenvalue at the double-zero critical point, the evaluation of the generalized Keldysh's eigenfunctions is required. Finally, some numerical results are shown and the bifurcation scenario of the beam is discussed.     

Non-linear modal properties of non-shallow cables

A non-linear mechanical model of non-shallow linearly elastic suspended cables is employed to investigate the non-linear modal characteristics of the free planar motions. An asymptotic analysis of the equations of motion is carried out directly on the partial-differential equations overcoming the drawbacks of a discretization process. The direct asymptotic treatment delivers the approximation of the individual non-linear normal modes. General properties about the non-linearity of the in-plane modes of different type—geometric, elasto-static and elasto-dynamic—are unfolded. The spatial corrections to the considered linear mode shape caused by the quadratic geometric forces are investigated for modes belonging to the three mentioned classes. Moreover, the convergence of Galerkin reduced-order models is discussed and the influence of passive modes is highlighted.     

A Fast and Effective Method for Packing Nano-LC Columns with Solid-Core Nano Particles Based on the Synergic Effect of Temperature, Slurry Composition, Sonication and Pressure

Nano-LC columns of different lengths (14–35 cm), 75 μm i.d., were packed with solid-core C18 particles using a conventional HPLC system at low pressure (375 bar) and without expensive tools and fittings. Solid-core particles consist of a solid, non-porous core surrounded with a shell of a porous layer with a very narrow particle size distribution. This geometry allows a faster diffusion of the analytes compared to porous particles, reducing the C term of the Knox plot. Different slurries of packing material were evaluated and tested. The packing procedure was carried out at room temperature and at 70 °C to evaluate the influence of this parameter on the overall process. The synergic action of pressure, temperature and sonication contributed to columns of various lengths in the packing process. The columns were tested at room temperature taking into account the following parameters: Knox plots, specific permeability and peak capacity. Reduced heights of theoretical plates, h, ranged between 3.8 and 5.1 at ν between 2 and 6. An LC-MS test was carried out with a Direct-EI LC-MS instrument.