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81.
Dipl.‐Chem. Alexander Rupp Dr. Nataliya Roznyatovskaya Dr. Harald Scherer Dr. Witali Beichel Petra Klose Carola Sturm Dr. Anke Hoffmann Dr. Jens Tübke Prof. Dr. Thorsten Koslowski Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9794-9804
Several, partly new, ionic liquids (ILs) containing imidazolium and ammonium cations as well as the medium‐sized [NTf2]? (0.230 nm3; Tf=CF3SO3?) and the large [Al(hfip)4]? (0.581 nm3; hfip=OC(H)(CF3)2) anions were synthesized and characterized. Their temperature‐dependent viscosities and conductivities between 25 and 80 °C showed typical Vogel–Fulcher–Tammann (VFT) behavior. Ion‐specific self‐diffusion constants were measured at room temperature by pulsed‐gradient stimulated‐echo (PGSTE) NMR experiments. In general, self‐diffusion constants of both cations and anions in [Al(hfip)4]?‐based ILs were higher than in [NTf2]?‐based ILs. Ionicities were calculated from self‐diffusion constants and measured bulk conductivities, and showed that [Al(hfip)4]?‐based ILs yield higher ionicities than their [NTf2]? analogues, the former of which reach values of virtually 100 % in some cases.From these observations it was concluded that [Al(hfip)4]?‐based ILs come close to systems without any interactions, and this hypothesis is underlined with a Hirshfeld analysis. Additionally, a robust, modified Marcus theory quantitatively accounted for the differences between the two anions and yielded a minimum of the activation energy for ion movement at an anion diameter of slightly greater than 1 nm, which fits almost perfectly the size of [Al(hfip)4]?. Shallow Coulomb potential wells are responsible for the high mobility of ILs with such anions. 相似文献
82.
Dr. Jamie Hicks Dr. Petra Vasko Andreas Heilmann Prof. Jose M. Goicoechea Prof. Simon Aldridge 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20556-20560
The reactivity of the electron-rich anionic AlI aluminyl compound K2[(NON)Al]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) towards mono- and disubstituted arenes is reported. C−H activation chemistry with n-butylbenzene gives exclusively the product of activation at the arene meta position. Mechanistically, this transformation proceeds in a single step via a concerted Meisenheimer-type transition state. Selectivity is therefore based on similar electronic factors to classical SNAr chemistry, which implies the destabilisation of transition states featuring electron-donating groups in either ortho or para positions. In the cases of toluene and the three isomers of xylene, benzylic C−H activation is also possible, with the product(s) formed reflecting the feasibility (or otherwise) of competing arene C−H activation at a site which is neither ortho nor para to a methyl substituent. 相似文献
83.
Sabine Apelt Susanne Höhne Petra Uhlmann Ute Bergmann 《Surface and interface analysis : SIA》2020,52(12):1150-1155
Active deicing of technical surfaces, such as for wind turbines and heat exchangers, currently requires the usage of heat or chemicals. Passive coating strategies that postpone the freezing of covering water would be beneficial in order to save costs and energy. One hypothesis is that pyroelectric active materials can achieve this because of the surface charges generated on these materials when they are subject to a temperature change. High-quality poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) thin films with a high crystallinity, prefererd edge-on orientation, low surface roughness, and comprised of the β-analogous ferroelectric phase were deposited by spin-coating. Freezing experiments with a cooling rate of 1 K min−1 were made on P(VDF-TrFE) coatings in order to separate the effect of different parameters such as the poling direction, film thickness, used solvent, deposition process, underlying substrate, and annealing temperature on the achievable supercooling. The topography and the underlying substrate significantly changed the distribution of freezing temperatures of water droplets in contact with these thin films. In contrast, no significant effect of the thickness, morphology, or pyroelectric effect of the as-prepared domain-state on the freezing temperatures was found. 相似文献
84.
Stefano Carli Wouter Dekeyser Reinart Coosemans Renaud Dejarnac Michael Komm Miglena Dimitrova Jiří Adámek Petra Bílková Petr Böhm 《等离子体物理论文集》2020,60(5-6):e201900155
Mean-field plasma edge transport codes such as SOLPS-ITER heavily rely on ad-hoc radial diffusion coefficients to approximately model anomalous transport. Such coefficients are experimentally determined and vary between different machines, and also depend on the operational regime and plasma location within the same device. Therefore, to match experimental data the modeller is required to manually tune several free parameters in expensive simulations, and the code's predictive capabilities are significantly downgraded. As a solution, a new model has been developed for SOLPS-ITER, solving an additional transport equation for the turbulent kinetic energy k, derived by consistently time-averaging the Braginskii equations, and including a diffusive closure for the anomalous particle flux. This closure model relates the anomalous diffusion coefficient to the local k value. The resulting equation structure and its closure are inspired by TOKAM2D isothermal interchange turbulence simulation results. Within this model, fewer and hopefully more universal free parameters are retained, thus improving the code's predictive capabilities. The new model has been tested on a COMPASS case for which upstream plasma profiles were available. Experimental data and a reference solution, obtained by matching the profiles through manual tuning of radial diffusivities, have been used to estimate the parameters of our new transport model. A ballooned particle diffusivity profile is retrieved by the new radial transport model, thanks to the proposed interchange drive. The obtained upstream profiles qualitatively agree with the experiment and prove the new model is a promising first attempt to be further refined. 相似文献
85.
Theodosis Giousis Georgia Potsi Antonios Kouloumpis Konstantinos Spyrou Yiannis Georgantas Nikolaos Chalmpes Konstantinos Dimos Myrsini‐Kiriaki Antoniou Georgios Papavassiliou Athanasios B. Bourlinos Hae Jin Kim Vijay Kumar Shankarayya Wadi Saeed Alhassan Majid Ahmadi Bart J. Kooi Graeme Blake Daniel M. Balazs Maria A. Loi Dimitrios Gournis Petra Rudolf 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2021,133(1):364-369
Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (Eg) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells. 相似文献
86.
The aim of this work was to investigate the influence of initial pH value (pH0) on the isothermal adsorption of Reactive Black 5 (RB5) dye on commercial powdered activated carbon. Four initial pH values were chosen for this experiment: pH0 = 2.00, 4.00, 8.00, and 10.00. In order to investigate the mechanism of adsorption kinetic, studies have been performed using pseudo-first-order and pseudo-second-order kinetic models as well as an intraparticle diffusion model. In addition, thermodynamic parameters of adsorption were determined for pH0 = 4.00. Results of this research showed that the initial pH value significantly influences the adsorption of RB5 dye onto activated carbon. The highest adsorption capacities (qe) and efficiencies of decolouration were observed for initial pH values of pH0 = 2.00 (qe = 246.0 mg g−1) and 10.00 (qe = 239.1 mg g−1) due to strong electrostatic interactions and attractive π···π interactions, respectively. It was also shown that the adsorption of RB5 dye on activated carbon at all initial pH values is kinetically controlled, assuming a pseudo-second-order model, and that intraparticle diffusion is not the only process that influences on the adsorption rate. 相似文献
87.
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89.
[reaction: see text] A new method for the synthesis of 2',3'-dideoxynucleoside analogues has been developed. An electrochemical activation of 2-substituted furans is followed by the coupling with a pyrimidine or purine base. This gives planar furyl nucleosides as key intermediates, which are hydrogenated cis-selectively to give the corresponding beta-2',3'-dideoxynucleosides as racemic mixtures. An enzymatic kinetic resolution gives rise to beta-D- and beta-L-configured derivatives in high optical purity. This is exemplified by the synthesis of beta-D- and beta-L-3'-deoxythymidine. 相似文献
90.
C. M. Dion P. Sjölund S. J.H. Petra S. Jonsell M. Nylén L. Sanchez-Palencia A. Kastberg 《The European physical journal. Special topics》2008,159(1):11-17
We study a Brownian motor, based on cold atoms in optical lattices, where atomic motion can be induced in a controlled manner
in an arbitrary direction, by rectification of isotropic random fluctuations. In contrast with ratchet mechanisms, our Brownian
motor operates in a potential that is spatially and temporally symmetric, in apparent contradiction to the Curie principle.
Simulations, based on the Fokker-Planck equation, allow us to gain knowledge on the qualitative behaviour of our Brownian
motor. Studies of Brownian motors, and in particular ones with unique control properties, are of fundamental interest because
of the role they play in protein motors and their potential applications in nanotechnology. In particular, our system opens
the way to the study of quantum Brownian motors. 相似文献