X-ray diffraction and theoretical studies for the quantitative assessment of intermolecular arene-perfluoroarene stacking interactions

The arene-perfluoroarene stacking interaction was studied by experimental and theoretical methods. A series of compounds with different possibilities for formation of this recognition motif in the solid state were synthesized, and their crystal structures determined by single-crystal X-ray diffraction. The crystal packing of these compounds, as well as the packing of related compounds retrieved from crystallographic databases, were analyzed with quantitative crystal potentials: total lattice energies and the cohesive energies of closest molecular pairs in the crystals were calculated. The arene-perfluoroarene recognition motif emerges as a dominant interaction in the non-hydrogen-bonding compounds studied here, to the point that asymmetric dimers formed over the stacking motif carry over to asymmetric units made of two molecules in the crystal both for pure compounds and for molecular complexes; however, inter-ring distances and angles range from 3.70 to 4.85 A and from 5 to 21 degrees , respectively. Pixel energy partitioning reveals that whenever aromatic rings stack, the largest cohesive energy contribution comes from dispersion, which roughly amounts to 20 kJ mol(-1) per phenyl ring, while the coulombic term is minor but significant enough to make a difference between the arene-arene or perfluoroarene-perfluoroarene interactions on the one hand, and arene-perfluoroarene interactions on the other, whereby the latter are favored by about 10 kJ mol(-1) per phenyl ring. No evidence of special interaction which can be attributed to HF confrontation was recognizable.     

Keto-coumarin scaffold for photoinitiators for 3D printing and photocomposites

The purposes of this paper are moving toward (a) the development of a new series of photoinitiators (PIs) which are based on the keto-coumarin (KC) core, (b) the introduction of light-emitting diodes (LEDs) as inexpensive and safe sources of irradiation, (c) the study of the photochemical mechanisms through which the new PIs react using different techniques such as Fourier transform infrared, UV–visible or fluorescence spectroscopy, and so on, (d) the use of such compounds (presenting good reactivity and excellent photopolymerization initiating abilities) for two specific and high added value applications: 3D printing (@405 nm) and preparation of thick glass fiber photocomposites with excellent depth of cure, and finally (e) the comparison of the performance of these KC derivatives versus other synthesized coumarin derivatives. In this study, six well-designed KC derivatives ( KC-C , KC-D , KC-E , KC-F , KC-G , and KC-H ) are examined as high-performance visible-light PIs for the cationic polymerization of epoxides as well as the free-radical polymerization of acrylates upon irradiation with LED@405 nm. Excellent polymerization rates are obtained using two different approaches: a photo-oxidation process in combination with an iodonium (Iod) salt and a photo-reduction process when associated with an amine (N-phenylglycine or ethyl 4-(dimethylamino)benzoate). High final reactive conversions were obtained. A full picture of the involved photochemical mechanisms is provided.     

Comparison of analytical methods: ICP-QMS,ICP-SFMS and FF-ET-AAS for the determination of V,Mn, Ni,Cu, As,Sr, Mo,Cd and Pb in ground natural waters

Three analytical methods, namely, inductively coupled plasma sector field mass spectrometry (ICP-SFMS); inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and filter-furnace electrothermal atomic-absorption spectroscopy (FF-ET-AAS) for the determination of V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb in ground natural water samples were compared and evaluated for their capacity to provide reliable and precise results. Two certified reference materials (SLEW-3 Estuarine Water; SLRS-4 River Water) were analysed to prove that accurate results could be obtained by using all the listed methods with properly optimised parameters. The limit of detection (LOD) for V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb provided by the ICP-MS methods ranged from 0.001 to 0.05 µg L^?1. Such LOD proved sufficient for the reliable determination of the listed elements in ground natural waters. However, the LOD of the FF-ET-AAS was approximately two orders of magnitude higher than that of ICP-MS, which made it impossible to quantify V, Mn, Ni, Mo and Pb. The effects of the usage of the collision cell mode in ICP-QMS and of the desolvation system Apex for ICP-SFMS to eliminate oxide ions levels were investigated. For all three analytical methods, the influence of the matrix effect on the results of the determination of the investigated elements using matrix model solution, external calibration and standard addition methods was evaluated. A comparison using a paired Student’s t-test between the results obtained by both ICP-MS methods for V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb concentrations in ground natural waters showed that there was no significant difference on a 95% confidence level. The precision of the results for ICP-SFMS, ICP-QMS and FF-ET-AAS varied between ~0.5 and 11; 2.5 and 12.5; 3 and 13.5%, respectively. Moreover, ICP-SFMS equipped with the desolvation system APEX proved a better choice for As, Cu and Mn analysis due to its better LOD (0.008, 0.03 and 0.02 µg L^?1, respectively) and precision (S_r ≤ 5.0; 7.5; 9.0%, respectively) compared to ICP-QMS and FF-ET-AAS.     

Electronic structure of GaAs/A1GaAs quantum double rings in lateral electric field

A three-dimensional model of GaAs/A1GaAs quantum double rings in the lateral static electric field is investigated theoretically. The eigenvalue problem with the effective-mass approximation is solved by means of the finite-element method. The energy levels and wave functions of quantum-confined electrons and heavy holes are obtained and show an agreement with our previous theoretical and experimental studies. It is shown in the approximation of neglecting the Coulomb attraction between the electron and heavy hole that a relatively large Stark shift of exciton emission of 4 meV is attainable with an applied electric field of 0.7 kV/cm.     

Magnetic monopole search at high altitude with the SLIM experiment

The SLIM experiment was a large array of nuclear track detectors located at the Chacaltaya high altitude Laboratory (5230 m a.s.l.). The detector was in particular sensitive to intermediate mass magnetic monopoles, with masses 10⁵ GeV <M_M< 10¹² GeV. From the analysis of the full detector exposed for more than 4 years a flux upper limit of 1.3×10^-15 cm^-2 s^-1 sr^-1 for downgoing fast intermediate mass monopoles was established at the 90% C.L. PACS 14.80.Hv; 29.40.Wk; 29.90.+r     

Phase-locked analysis of velocity fluctuations in a turbulent free swirling jet after vortex breakdown

Large-scale organized vortical structures were studied experimentally in a free swirling jet of air experiencing vortex precession (PVC) at ambient conditions. Detailed measurements were performed in the region near the nozzle exit using phase-locked LDV and PIV, at a Reynolds number of Re ?? 24,400 and a swirl parameter S ?? 1.0. The investigation allowed reconstruction of the time-averaged flowfield, with the associated distribution of turbulent fluctuations, the phase-locked structure of the jet and the associated precessing vortex structure. An original joint analysis of power spectra and probability density functions of velocity data led to quantification of the PVC effect on turbulent fluctuations. This analysis showed that the PVC contribution can be properly separated from the background random turbulence, reproducing the results of phase-locked measurements. It is found that the background turbulence in the near field is substantially weaker if compared to the coherent fluctuations induced by vortex precession.     

Investigation of fine scale structure of turbulent and molecular diffusion in coaxial jets of He/CO2 in air by LDA and Rayleigh scattering

This paper revisits the important issue of differential diffusion and provides new experimental results and subsequent analysis that attempts to quantify the relationship between molecular diffusion, turbulent diffusion and their mutual interference in non-reacting axisymmetric coaxial jets of variable Reynolds number. The reported investigation has been focused on the analysis of molecular diffusion of a He/CO₂ mixture in air by combining line imaging of Rayleigh scattering and laser Doppler anemometry (LDA) to determine length scales associated with differential diffusion and turbulent transport. Line imaging Rayleigh scattering was performed applying the index-matching method with a mixture of two gaseous species having scattering cross-sections respectively lower and higher of that of air and the cross-section of the mixture identical to that of the co-flowing air. Any measured variation in scattering intensity is therefore due to differential diffusion between the two species. Instantaneous and ensemble averaged line profiles of Rayleigh scattering intensity are presented and a characteristic length scale associated with differential diffusion is deduced. Autocorrelation analysis is applied to obtain the characteristic scale of differential diffusion fluctuations and the integral length scales of velocity fluctuations, as measured by LDA. Theoretical information from the literature is used in relating these scales to the molecular and turbulent diffusion coefficients, assuming homogeneous and isotropic turbulence, and the ratio of molecular to turbulent diffusivity is estimated as a function of the Reynolds number. The results confirm that the average contribution of molecular diffusion to the effective diffusivity into the air stream progressively reduces when the turbulence level increases. They also suggest that, at higher Re, the differential diffusion remains significant down to the scalar dissipation length scale, and could influence mixing at the molecular level and thus chemical reactions.