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.     

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.     

Die Verwendung des elektrischen Stromes als W?rmequelle

Ohne Zusammenfassung     

Superconductivity of the graphite intercalation compounds KHgC8 and RbHgC8

Superconductivity was observed in the graphite intercalation compounds, KHgC₈ and RbHgC₈, using an AC induction technique. The transition temperatures were 1.90K and 1.44K for KHgC₈ and RbHgC₈ respectively. A full Meissner effect was observed for KHgC₈ with a temperature dependant anisotropy in critical field with a value of 25 ± 5 at T_c.     

Optical properties of stages 1 and 2 potassium mercurographitides

We have measured the reflectivity spectra of stages 1 and 2 graphite intercalated with KHg amalgam (KHgC₄ and KHgC₈) from 0.5–6eV, and compared them to the corresponding stages 1 and 2 binary compounds, KC₈ and KC₂₄. Plasma edges for the ternaries appear at about the same energies as in the binaries, but differences are observed in the reflectivity values at the minima. Kramers-Kroenig analysis yields thresholds for the onset of interband transitions at 1.3eV and 1.2eV for KHgC₄ and KHgC₈, compared to 2.7eV and 1.7eV for KC₈ and KC₂₄. The thresholds are explained in terms of interband transitions in the mercurographitides involving the Hg levels. A model for these transitions is presented based on the Mott metal-semiconductor transition in mercury. This model is shown to be consistent with the hypothesis that the mercury layers are negatively charged.     

Curriculum, Classroom Practices, and Tool Design in the Learning of Functions Through Technology-Aided Experimental Approaches

The paper starts from classroom situations about the study of a functional relationship with help of technological tools as a ‘transposition’ of experimental approaches from research mathematical practices. It considers the limitation of this transposition in existing curricula and practices based on the use of non-symbolic software like dynamic geometry and spreadsheets. The paper focuses then on the potentialities of classroom use of computer algebra packages that could help to go beyond this shortcoming. It looks at a contradiction: while symbolic calculation is a basic tool for mathematicians, curricula and teachers are very cautious regarding their use by students. The rest of the paper considers the design and experiment of a computer environment Casyopée as means to contribute to an evolution of curricula and classroom practices to achieve the transposition in the domain of algebraic activities linked to functions.     

Magnetic moments of the 12+ isomeric states in 194, 196, 198Pb

The g-factor of the 12⁺ isomeric state in lead isotopes with A = 194, 196, 198 was measured using the time-differential perturbed angular distribution method (TDPAD). The values obtained are respectively g(194) = ?0.158(6); g(196) = ?0.157(7); g(198) = ?0.144(11). A more precise determination of the 12⁺ level half-life is also made. The g-factprs of these nuclear states, which are described with v(i_{$\text{13}\text{2}$})^?2 as the main configuration, are surprisingly constant over a large mass range (between A = 206 and 194). A core polarization analysis explains this trend: the polarization induced on neutrons in i_{$\text{13}\text{2}$} orbit decreases with the mass number A (blocking effect), but a compensation is provided by the other spin-orbit partners f_{$\text{7}\text{2}$}-f_{$\text{5}\text{2}$} and P_{$\text{3}\text{2}$}-P_{$\text{1}\text{2}$}.