NH+-F hydrogen bonding in a fluorinated "proton sponge" derivative: integration of solution, solid-state, gas-phase, and computational studies

We report detailed studies on the characterization of an intramolecular NH-F hydrogen bond formed within a fluorinated "proton sponge" derivative. An ammonium ion, generated from 8-fluoro-N,N-dimethylnaphthalen-1-amine, serves as a charged hydrogen bond donor to a covalently bound fluorine appropriately positioned on the naphthalene skeleton. Potentiometric titrations of various N,N-dimethylnaphthalen-1-amines demonstrate a significant increase in basicity when hydrogen bonding is possible. X-ray crystallography reveals that NH-F hydrogen bonding in protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine is heavily influenced by ion pairing in the solid state; bifurcated and trifurcated hydrogen bonds are formed depending on the counterion utilized. Compelling evidence of hydrogen bonding in the 8-fluoro-N,N-dimethylnaphthyl-1-ammonium cation is provided by gas-phase cryogenic vibrational photodissociation spectroscopy. Solution-phase infrared spectroscopy provides complementary results, and the frequencies of the N-H stretching mode in both phases are in excellent agreement with the computed vibrational spectra. NMR analysis of protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine demonstrates significant H-F coupling between the N-H hydrogen and fluorine that cannot be attributed to long-range, through-bond interactions; the couplings correlate favorably with calculated values. The results obtained from these experiments are congruent with the formation of an NH-F hydrogen bond upon protonation of 8-fluoro-N,N-dimethylnaphthalen-1-amine.     

Selective conversion of {Mo132} Keplerate ion into 4-electron reduced crown-capped Keggin derivative [Te5Mo15O57](8-). A key intermediate to single-phase M1 multielement MoVTeO light-alkanes oxidation catalyst

{Mo(132)} Keplerate anion reacts with tellurites to give a soluble precursor to produce in hydrothermal conditions single-phase M1 MoVTeO light-alkanes oxidation catalyst. Characterization of this Te-containing intermediate by single-crystal X-ray diffraction, (125)Te NMR, UV-visible and redox titration reveals a molybdotellurite anion as a crown-capped Keggin derivative.     

Rheo-attenuated total reflectance infrared spectroscopy: a new tool to study biopolymers

Whilst rheology is the reference technique to study the mechanical properties of unspun silk, we know little of the structure and the dynamics that generate them. By coupling infrared spectroscopy and shearing forces to study silk fibroin conversion, we are introducing a novel tool to address this gap in our knowledge. Here the silk conversion process has been studied dynamically using polarized attenuated total reflectance Fourier transform infrared spectroscopy whilst applying shear, thus revealing silk protein conformation and molecular orientation in situ. Our results show that the silk conversion process starts with a pre-alignment of the proteins followed by a rapid growth of the β-sheet formation and then a subsequent deceleration of the growth. We propose that this tool will provide further insight into not only silk but any biopolymer solution, opening a new window into biological materials.     

Carbon dioxide flow boiling in a single microchannel - Part I: Pressure drops

Carbon dioxide two-phase flow pressure drops have been investigated in a single horizontal stainless-steel micro-tube having a 0.529 mm inner diameter. Experiments were carried out in adiabatic conditions for four saturation temperatures of −10; −5; 0; 5 °C and mass fluxes ranging from 200 to 1400 kg/m² s, for inlet qualities up to unity. Measurements have been compared to the predictions of well-known methods. The Müller-Steinhagen and Heck correlation and the Friedel correlation gave the best fit as well as the homogeneous model when the liquid viscosity is used to represent the apparent two-phase viscosity. Further, an analysis based on the homogeneous model has not shown any clear appearance of the laminar or the transition regimes in any given range of Reynolds number. The apparent viscosity of the two-phase mixture was found larger than the liquid viscosity at low vapour qualities, namely at the lowest temperatures. Hence, a new expression to determine the equivalent viscosity was suggested as a function of the reduced pressure. Lastly, the Chisholm parameter from the Lockhart-Martinelli correlation was found lower than expected and also mainly dependent on the saturation temperature.     

Optimized absorption imaging of mesoscopic atomic clouds

We report on the optimization of high-intensity absorption imaging for small Bose–Einstein condensates. The imaging calibration exploits the linear scaling of the quantum projection noise with the mean number of atoms for a coherent spin state. After optimization for atomic clouds containing up to 300 atoms, we find an atom number resolution of $\varDelta_{\rm det}= 3.7$ atoms, mainly limited by photon shot noise and radiation pressure.     

Laser-induced incandescence technique to identify soot nucleation and very small particles in low-pressure methane flames

This paper presents the study we carried out on the formation of soot particles in low-pressure premixed CH₄/O₂/N₂ flames by using Laser-Induced Incandescence (LII). Flames were stabilised at 26.6 kPa (200 torr). Four different equivalence ratios were tested (Φ = 1.95, 205, 2.15 and 2.32), Φ = 1.95 corresponding to the equivalence ratio for which LII signals begin to be measurable along the flame. The evolution of the LII signals with laser fluence (fluence curve), time (temporal decay) and emission wavelength is reported at different heights above the burner. We specifically took advantage of the low-pressure conditions to probe with a good spatial resolution the soot inception zone of the flames. Significant different behaviours of the fluence curves are observed according to the probed region of the flames and Φ. In addition, while the surface growth process is accompanied by an increase in the LII decay-times (indicator of the primary particle diameter) at higher Φ, decay-times become increasingly short at lower Φ reaching a constant value along the flame at Φ = 1.95. These behaviours are consistent with the detection of the smallest incandescent particles in the investigated flames, these particles having experienced very weak surface growth. Flame modelling including soot formation has been implemented in flames Φ = 2.05 and 2.32. Experimental quantitative soot volume fraction profiles were satisfactorily reproduced by adjusting the fraction of reactive soot surface available for reactions. The qualitative variation of the computed soot particle diameter and the relative weight of surface growth versus nucleation were consistent with the experimental observations.     

Rotation Numbers of Discontinuous Orientation-Preserving Circle Maps

We extend a few well-known results about orientation preserving homeomorphisms of the circle to orientation preserving circle maps, allowing even an infinite number of discontinuities. We define a set-valued map associated to the lift by filling the gaps in the graph, that shares many properties with continuous functions. Using elementary set-valued analysis, we prove existence and uniqueness of the rotation number, periodic limit orbit in the case when the latter is rational, and Cantor structure of the unique limit set when the rotation number is irrational. Moreover, the rotation number is found to be continuous with respect to the set-valued extension if we endow the space of such maps with the Haussdorff topology on the graph. For increasing continuous families of such maps, the set of parameter values where the rotation number is irrational is a Cantor set (up to a countable number of points).     

Convergence of the wave equation damped on the interior to the one damped on the boundary

In this paper, we study the convergence of the wave equation with variable internal damping term γn(x)ut to the wave equation with boundary damping γ(x)⊗δx∈∂Ωut when (γn(x)) converges to γ(x)⊗δx∈∂Ω in the sense of distributions. When the domain Ω in which these equations are defined is an interval in R, we show that, under natural hypotheses, the compact global attractor of the wave equation damped on the interior converges in X=H¹(Ω)×L²(Ω) to the one of the wave equation damped on the boundary, and that the dynamics on these attractors are equivalent. We also prove, in the higher-dimensional case, that the attractors are lower-semicontinuous in X and upper-semicontinuous in H1−ε(Ω)×H−ε(Ω).     

Micellar Solubilization of Proteins in Aprotic Solvents and their Spectroscopic Characterisation

The quaternary ammonium salt methyl-trioctylammonium chloride enables the transfer of α-chymotrypsin, trypsin, pepsin and glucagone from water to cyclohexane. Reversed micelles, whose polar core solubilizes both protein and water, are probably formed in the apolar phase. The influence of various parameters on the phase transfer (concentration, pH, solvent, temperature, etc.) has been investigated. Absorption, fluorescence and circular dichroism studies of the biopolymers in the cyclohexane system have been carried out. For trypsin and chymotrypsin, the CD. signal in the 200 nm region is very similar in water and in cyclohexane, which suggests that the polypeptide folding is not substantially different in the two phases. The fluorescence quantum yield is always much larger in the cyclohexane phase than in water. The longer wavelength region of the UV. absorption spectrum is slightly red-shifted relative to water, and a band at 225 nm, probably arising from the aromatic chromophore, is apparent in the organic phase. Reasons for these spectral perturbations are discussed. The enzymes transferred from water into cyclohexane phases can be continuously retransferred into a second water phase. The possible relevance of this ‘double transfer’ as a model for the vectorial transport of biopolymers or a separation technique is discussed.