Regioselectivity of fluorine substitution by alkoxides on unsymmetrical difluoroarenes

An efficient approach to unsymmetrical halogenated resorcinol diethers has been developed. This synthesis consists of two subsequent nucleophilic aromatic substitutions (S_NAr) of unsymmetrical difluoroarenes by alkoxides. The novelty of this approach is its control of regioselectivity during the first S_NAr, which occurs at room temperature. Interestingly, the reactivity of competing fluorines was correlated to their chemical shift in ¹⁹F NMR.     

An experimental and kinetic modeling study on the oxidation of 1,3-dioxolane

The modern catalytic or enzymatic advances allow the production of novel biofuel. Among them, 1,3-dioxolane can be produced from formaldehyde and ethylene glycol, both can be obtained from biomass. In this study, the oxidation of 1,3-dioxolane is studied at stoichiometric conditions. The ignition delay times of 1,3-dioxolane/O₂/inert mixtures were measured in a shock tube and in a rapid compression machine at pressures of 20 to 40 bar and temperatures ranging from 630 to 1300 K. The pressure profiles recorded in the rapid compression machine show a first stage of ignition enlightening the influence of the low temperature chemistry of combustion. Furthermore, mole fraction profiles of the stable intermediates produced during the oxidation of 1,3-dioxolane were measured in a jet-stirred reactor at 10 bar. Following these observations, a detailed kinetic model was developed with reaction rate coefficients and thermochemical data calculated by theoretical calculations or estimated by analogies to suitable molecules. In order to get an insight into the most important reaction pathways brute force sensitivity analysis and reaction pathway analysis were performed with the proposed model and discussed. It became clear that in the fuel-in-air case for the alkylhydroperoxide of 1,3-dioxolane the ring opening beta-scission pathway is favored against the further alkane-like second addition to molecular oxygen, which leads to a limited negative temperature coefficient.     

Combined FRM and GDFT filter bank designs for improved nonuniform DSA channelisation

Multistandard channelisation for base stations is a big application of generalised discrete Fourier transform modulated filter banks (GDFT‐FBs) in digital communications. For technologies such as software‐defined radio and cognitive radio, nonuniform channelisers must be used if frequency bands are shared by different standards. However, GDFT‐FB‐based nonuniform channelisers can suffer from high filter orders when applied to wideband input signals. In this paper, various combinations of GDFT‐FB with the frequency response masking technique are proposed and evaluated for both uniform and nonuniform channelisation applications. Results show that the proposed techniques achieve savings in both the number of filter coefficients and the number of operations per input sample. Copyright © 2015 John Wiley & Sons, Ltd.     

A field deployable method for a rapid screening analysis of inorganic arsenic in seaweed

Inorganic arsenic (iAs) in 13 store-bought edible seaweed samples and 34 dried kelp (Laminaria digitata) samples was determined by a newly developed, field-deployable method (FDM) with the aid of a field test kit for arsenic in water. Results from the FDM were compared to results from speciation analysis achieved by using high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The FDM consisted of a simple extraction method using diluted HNO₃ to quantitatively extract iAs without decomposing the organoarsenicals to iAs followed by the selective volatilisation of iAs as arsine (AsH₃) and subsequent chemo-trapping on a filter paper soaked in mercury bromide (HgBr₂) solution. Method optimization with a sub-set of samples showed 80–94% iAs recovery with the FDM with no matrix effect from organo-arsenic species in the form of dimethylarsinic acid (DMA) on the iAs concentration. The method displayed good reproducibility with an average error of ±19% and validation by HPLC-ICP-MS showed that the results from the FDM were comparable (slope = 1.03, R² = 0.70) to those from speciation analysis with no bias. The FDM can be conducted within an hour and the observed limit of quantification was around 0.05 mg kg^?1 (dry weight). This method is well suited for on-site monitoring of iAs in seaweed before it is harvested and can thus be recommended for use as a screening method for iAs in seaweed.

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Graphical abstract Screening seaweed for their inorganic arsenic concentration within one hour without bias has been made possible in the field by using a field deployable arsenic kit. Its accuracy and precision was compared to HPLC-ICPMS.

     

The non-Gaussian dynamics of glycerol

We have combined incoherent quasielastic neutron scattering experiments and atomistic molecular simulations to investigate the microscopic dynamics of glycerol moving away from the hydrodynamic limit. We relate changes in the momentum transfer (Q) dependence of the relaxation time to distinct changes of the single-particle dynamics. Going from small to large values of Q, a first crossover at about 0.5 ?(-1) is related to the coupling of the translational diffusion dynamics to the non-Debye structural relaxation, while the second crossover at a Q-value near the main diffraction peak is associated with the Gaussian to non-Gaussian crossover of the short-time molecular dynamics, related to the decaging processes. We offer an unprecedented extension of previous studies on polymeric systems towards the case of the typical low-molecular-weight glass-forming system glycerol.     

Pulse compression and fiber delivery of 45 fs Fourier transform limited pulses at 830 nm

A specific scheme is used for fiber delivery of ultrashort pulses using conventional elements. Starting from a standard femtosecond Ti:Al(2)O(3) oscillator (150 fs @ 830 nm), perfectly compressed ultrashort pulses with a duration of 45 fs are produced at the output of a standard two meter long single-mode fiber. The setup allows compensating independently and simultaneously second and third orders of chromatic dispersion as well as management of self-phase modulation in the fiber. It includes an optimized dispersion compensation line made of the assembly of diffraction gratings and prisms. The unsurpassed performances of the device are experimentally and numerically highlighted. Fiber delivery of sub-30 fs multinanojoule pulses is discussed.     

Fast intramolecular dynamics of triphenyl phosphite investigated by <Emphasis Type="Bold">2</Emphasis>H NMR

The first analysis of rapid intramolecular motions of triphenyl phosphite by ²H NMR is presented. The fragile slowing down of the primary relaxation is followed by a solid-echo method. The occurrence of a fast reorientation of the phenyl side groups is demonstrated in the supercooled liquid state, identified as a two-fold flip on the basis of simple lineshape simulations. Coexistence of both static and motionally averaged components in “two phase” spectra indicate a broad distribution of correlation times for this relaxation. This dynamical behavior is shown to persist in the glacial phase. Received 28 May 2002 / Received in final form 1st October 2002 Published online 31 December 2002