Experimental study of the growth of cholesteric fingers subjected to an AC electric field and a temperature gradient

We study the behaviour of cholesteric fingers of the first and second types (CF1 and CF2, respectively) which form in cholesteric samples treated for homeotropic anchoring when they are subjected to the combined action of an AC electric field and a temperature gradient. We investigate under which conditions each type of finger can drift and form a spiral. We then show that the ends of the growing CF1 follow circular trajectories, the curvatures of which depend linearly on the temperature gradient. This observation opens the possibility of measuring the thermal Lehmann coefficient in any cholesteric liquid crystal at all temperatures.     

Synthesis and structures of heteroleptic silylenes

The reaction of benzamidinato silicon trichloride [{PhC(NR)2}SiCl3] [R = Bu(t) (1), SiMe3 (2)] with 2 equiv of potassium in THF afforded mononuclear chlorosilylene [{PhC(NBu(t))2}SiCl] (3) and [{PhC(NSiMe3)2}2SiCl2] (4), respectively. Compound 4 was formed by the disproportionation of unstable [{PhC(NSiMe3)2}SiCl]. The reaction of [{PhC(NBu(t))2}SiCl3] (1) with 1 equiv of LiR (R = NMe2, OBu(t), OPr(i), PPr(i)2) in THF yielded [{PhC(NBu(t))2}SiCl2R] [R = NMe2 (5), OBu(t) (6), OPr(i) (7), PPr(i)2 (8)]. Treatment of 5-8 with 2 equiv of potassium in THF resulted in the novel heteroleptic silylene [{PhC(NBu(t))2}SiR] [R = NMe2 (9), OBu(t) (10), OPr(i) (11), PPr(i)2 (12)]. Compounds 4, 9, and 12 have been analyzed by X-ray crystallography.     

Water-soluble polymers as chelating agents for the deposition of Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>:LiNbO<Subscript>3</Subscript> waveguiding films

Compared to other oxide materials, the sol-gel deposition of an optically transparent LiNbO₃ waveguiding film of sufficient thickness (approx. 1?μm) is complicated by the presence of a highly hydrolyzing Nb(V) in the starting solution. Thicker films require more concentrated solutions that are not easily achieved for such ions. This problem may be solved using strong chelating agents such as water-soluble polymers. To prepare a stable Er(III)/Yb(III)/Li(I)/Nb(V)/2-methoxyethanol solution with high metal concentration, we tested three such polymers: polyethylene glycol (PEG), polyacrylic acid (PAA) and polyvinyl alcohol (PVA), and compared them with already used polyvinylpyrrolidone (PVP). The solutions were spin-coated on crystalline sapphire substrates under a multi-step heating-deposition regime. Apart from Er³⁺/Yb³⁺ photoluminescence properties, we evaluated the influence of the film microstructure (SEM, AFM) on optical transparency and waveguiding ability in the UV/Vis/NIR region (transmission and m-line spectroscopy). Among the newly tested polymers, only PEG was able to prevent Nb(V) hydrolysis up to a maximum metal concentration of 0.6?mol/L. For PEG and PVP, the crystallization temperature of the deposited films (between 700?°C and 1000?°C) was compared. After further optimization of the heating-deposition process, we were able to prepare a transparent Er³⁺/Yb³⁺:LiNbO₃ film thick enough to guide an optical signal in the NIR region. Thus, the use of PEG results is one of the very few non-hydrolytic sol-gel methods suitable for the preparation of not only luminescent, but also waveguiding Er³⁺/Yb³⁺:LiNbO₃ structures.

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Trinuclear Rhodium Complexes and Their Relevance for Asymmetric Hydrogenation

Various trinuclear rhodium complexes of the type [Rh₃(PP)₃(μ₃‐OH)_x(μ₃‐OMe)_2?x]BF₄ (where PP=Me‐DuPhos, dipamp, dppp, dppe; different ligands and μ‐bridging anions) are presented, which are formed upon addition of bases such as NEt₃ to solvate complexes [Rh(PP)(solvent)₂]BF₄. They were extensively characterized by X‐ray diffraction and NMR spectroscopy (¹⁰³Rh, ³¹P, ¹³C, ¹H). Their in situ formation resulting from basic additives (NEt₃) or basic prochiral olefins (without addition of another base) can cause deactivation of the asymmetric hydrogenation. This effect can be reversed by means of acidic additives.     

Zigzag instability of a χ disclination line in a cholesteric liquid crystal

We studied the formation of χ disclination lines in planar cholesteric samples placed in a temperature gradient near the cholesteric to smectic A phase transition. We observed that the first simple line which forms close to the smectic-cholesteric front zigzags when it is perpendicular to the direction of planar anchoring and is straight for other orientations. This instability is similar to Herring instability for crystalline surfaces. We show numerically that it originates from a strong increase of the elastic anisotropy close to the transition. In addition, we propose a new method to measure the pitch divergence at the smectic to cholesteric phase transition.     

A new network model for the integer quantum Hall effect

A Landauer–Büttiker-type formulation of backscattering between pairs of opposite directed channels is used to describe the coupling at the nodes of a network. Physically, these nodes correspond to saddle points of a slowly varying lateral potential modulation in a 2D electron system in the high magnetic field regime. We show that the network can be solved without needing a transfer matrix as used by Chalker and Coddington. We use an exponential dependence of the coupling on the filling factor of the associated Landau level. We demonstrate that our network representation allows a quantitative modeling of almost every realistic sample geometry in the quantum Hall regime, including the effect of gate electrodes across a Hall bar.     

Performance of a contour-based classification method for whistles of Mediterranean delphinids

Whistles from five delphinid species in the western Mediterranean Sea (Stenella coeruleoalba, Grampus griseus, Delphinus delphis, Tursiops truncatus, Globicephala melas) were taken from GREC sound archives. FFT contours (window size 512, Hanning, sampling frequency 44.1 kHz) were extracted with custom developed Matlab software: 277 samples of striped dolphins (Sc), 158 whistles of Risso’s dolphins (Gg), 120 of common dolphins (Dd), 76 of bottlenose dolphins (Tt), and 66 of pilot whales (Gm) were selected. Seafox software extracted 15 variables from the digitized contours, including: duration, initial, final, maximal and minimal frequency slopes, frequency range, number of frequency extrema, beginning, ending, maximal and minimal frequencies, presence of harmonics. Four of five species were significantly different (Mann-Whitney test) for average durations (respectively 0.73, 0.65, 0.47 and 0.89 s for Sc, Gg, Dd, Gm) while the average duration of bottlenose dolphins was 0.71 s. Frequency ranges (respectively 7.3, 6.3, 4.6, 3.2 and 6.3 kHz) were significantly different for all species pairs, with the exception of bottlenose and Risso’s dolphins. From a global point of view, pilot whale calls were the most distinct, with 43 significant pair-wise tests out of a total of 52, followed by the common dolphins. Risso’s dolphins were closest to other species whistles. A CART classification method achieved a global classification rate of 62.9%.     

A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization

The debate on the mechanism of dithiobenzoate-mediated RAFT polymerization may be overcome by taking the so-called “missing step” reaction between a highly reactive propagating radical and the three-arm star-shaped product of the combination reaction of an intermediate RAFT radical and a propagating radical into account. The “missing step” reaction transforms a propagating radical and a not overly stable three-arm star species into a resonance-stabilized RAFT intermediate radical and a stable polymer molecule. The enormous driving force behind the “missing step” reaction is estimated via DFT calculations of reaction enthalpies and reaction free enthalpies.