Thorough small‐angle X‐ray scattering analysis of the instability of liquid micro‐jets in air

Liquid jets are of interest, both for their industrial relevance and for scientific applications (more important, in particular for X‐rays, after the advent of free‐electron lasers that require liquid jets as sample carrier). Instability mechanisms have been described theoretically and by numerical simulation, but confirmed by few experimental techniques. In fact, these are mainly based on cameras, which is limited by the imaging resolution, and on light scattering, which is hindered by absorption, reflection, Mie scattering and multiple scattering due to complex air/liquid interfaces during jet break‐up. In this communication it is demonstrated that synchrotron small‐angle X‐ray scattering (SAXS) can give quantitative information on liquid jet dynamics at the nanoscale, by detecting time‐dependent morphology and break‐up length. Jets ejected from circular tubes of different diameters (100–450 µm) and speeds (0.7–21 m s^?1) have been explored to cover the Rayleigh and first wind‐induced regimes. Various solvents (water, ethanol, 2‐propanol) and their mixtures have been examined. The determination of the liquid jet behaviour becomes essential, as it provides background data in subsequent studies of chemical and biological reactions using SAXS or X‐ray diffraction based on synchrotron radiation and free‐electron lasers.     

Lithium solvation and diffusion in the 1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid

The Raman spectra of (1 − x)(BMITFSI), xLiTFSI ionic liquids, where 1‐butyl‐3‐methylimidazolium cation (BMI⁺) and bis(trifluoromethane‐sulfonyl)imide anion (TFSI⁻) are analyzed for LiTFSI mole fractions x < 0.4. As expected from previous studies on similar TFSI‐based systems, most lithium ions are shown to be coordinated within [Li(TFSI)₂]⁻ anionic clusters. The variation of the self‐diffusion coefficients of the ¹H, ¹⁹F, and ⁷Li nuclei, measured by pulsed‐gradient spin‐echo NMR (PGSE‐NMR) as a function of x, can be rationalized in terms of the weighted contribution of BMI⁺ cations, TFSI⁻ ‘free’ anions, and [Li(TFSI)₂]⁻ anionic clusters. This implies a negative transference number for lithium. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and ab initio study of the conformational isomerism in the 1‐ethyl‐3‐methyl‐imidazolium bis(trifluoromethanesulfonyl)imide ionic liquid

The calculated and experimental Raman spectra of the (EMI⁺)TFSI⁻ ionic liquid, where EMI⁺ is the 1‐ethyl‐3‐methylimidazolium cation and TFSI⁻ the bis(trifluoromethanesulfonyl)imide anion, have been investigated for a better understanding of the EMI⁺ and TFSI⁻ conformational isomerism as a function of temperature. Characteristic Raman lines of the planar (p) and non‐planar (np) EMI⁺ conformers are identified using the reference (EMI⁺)Br⁻ salt. The anion conformer of C₂ symmetry is confirmed to be more stable than the cis (C₁) one by 4.5 ± 0.2 kJ mol⁻¹. At room temperature, the population of trans (C₂) anions and np cations is 75 ± 2% and 87 ± 4%, respectively. Fast cooling quenches a metastable glassy phase composed of mainly C₂ anion conformers and p cation conformers, whereas slow cooling gives a crystalline phase composed of C₁ anion conformers and of np cation conformers. Copyright © 2006 John Wiley & Sons, Ltd.     

An experimental and theoretical study on the preparation of 4,4′‐methylene‐bis(N,N‐dimethylaniline) in ionic liquid

The reaction of N,N‐dimethylaniline with tetrachloromethane in ionic liquid was found to give 4,4′‐methylene‐bis (N,N‐dimethylaniline) in considerable yield. The ionic liquid was prepared from N,N‐dimethylaniline which is also the one of raw materials for the preparation of 4,4′‐methylene‐bis (N,N‐dimethylaniline), and acts as both solvent and catalyst in the reaction. Mild reaction conditions, enhanced rates, improved yields, and reagents' reactivity which is different from that in conventional organic solvents are the remarkable features observed in ionic liquids. In addition, the results of calculations are in good accordance with the experimental outcomes. Copyright © 2016 John Wiley & Sons, Ltd.     

Microscopic evidence of a metallic state in the one‐pot organic conductor ammonium tetrathiapentalene carboxylate

¹H NMR (nuclear magnetic resonance) and high‐field ESR (electron spin resonance) measurements were carried out for self‐doped organic conductors in the ammonium tetrathiapentalene carboxylate (TTPCOO)₂[(NH₄¹⁺)_1–x(NH₃⁰)_x ] system. While the pristine TTPCOOH molecule is closed‐shell, self‐doped carriers are generated by substitution of the carboxyl proton by (NH₃⁰) and (NH₄¹⁺), which can be regarded as a charge reservoir. The π‐extended system TTPCOO has a uniaxial g ‐tensor, indicating a 2D isotropic structure such as a herring‐bone‐like or parallel cross donor arrangement. The NMR‐relaxation rate indicated the Korringa relation in the temperature dependence, and the ESR linewidth followed the Elliot mechanism. Both of these observations provide supporting evidence for a stable metallic state. In this paper, we introduce self‐doped organic conductors as a branch of materials design, and emphasize that advanced magnetic resonance measurements are powerful tools for developing functional materials. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)