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41.
Magnus Pfaffenbach Dipl.‐Wirtschaftsing. Alexander Roller Prof. Dr. Tanja Gaich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(25):8444-8447
Herein, we report the synthetically practical, short, and general access to novel indolophane architectures by means of a photochemical C?H activation process—the Witkop cyclization. These highly strained scaffolds were obtained by photoinduced ring closure and feature atropisomerism as well as aromatic ring current effects, which both have been investigated. The prevailing regioselectivity of theWitkop cyclization reaction was completely reversed by the presence of a quaternary carbon center, exerting a strong Thorpe–Ingold effect on the system for which experimental‐evidence is provided. 相似文献
42.
Xia Li Gang-Hua Deng Rong-Juan Feng Ke Lin Zhen Zhang Yu Ba Zhou Lu Yuan Guo 《中国化学快报》2016,27(4):535-539
The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data. 相似文献
43.
Penetration by a cone into snow is commonly used to characterize snow properties. However, the effects of the diameter and half-angle of the cone on the mechanical properties of snow have not been systematically studied. In addition, no estimation of material parameters in a physically-based model has been made such that the results from penetration provide only an index of snow properties. In this paper, modeling and experimental methods are used to examine the effects of cone geometry on the maximum penetration force and associated hardness, with penetrometers ranging from 2.5 to 4 mm in diameter, 15° to 45° in cone half-angle, and testing both fine-grained and coarse-grained snows. The material point method, in conjunction with the Drucker–Prager cap plasticity model, was used to obtain the theoretical penetration force-distance relationship. Global sensitivity studies were conducted that indicate that the cohesion accounts for 86% of the penetration force, followed distantly by friction angle which accounts for 27%. A general trend, for the simulation results was established: for a given half-angle, the penetration force increases with the increase of diameter which holds for most of the test data as well; for a given diameter, the penetration force decreases with the increase of half-angle, which holds for some of the test data. In addition, for a given half-angle, the hardness decreases with the increase of diameter; for a given diameter, the hardness decreases with the increase of half-angle. To take into consideration the uncertainty of test data, a simple interval-based metric was used to compare test data with simulation results; the comparison was satisfactory. The material parameters from the simulations can thus be considered as calibrated ones for the snow studied. 相似文献
44.
Cover Picture: Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention (Angew. Chem. Int. Ed. 30/2015) 下载免费PDF全文
45.
Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl 下载免费PDF全文
Christoph Schnegelsberg Sebastian Bachmann Marlene Kolter Thomas Auth Dr. Michael John Prof. Dr. Dietmar Stalke Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7752-7762
Grignard reagents RMgCl and their so‐called turbo variant, the highly reactive RMgCl?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity‐enhancing effect. A combination of electrospray‐ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion‐ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron‐rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents. 相似文献
46.
Importance of the Correlation between Width and Length in the Shape Analysis of Nanorods: Use of a 2D Size Plot To Probe Such a Correlation 下载免费PDF全文
Prof. Clément Roux Dr. Céline Delmas Prof. Jean‐Daniel Marty Dr. Myrtil L. Kahn Dr. Christophe Mingotaud 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12424-12429
Analysis of nanoparticle size through a simple 2D plot is proposed in order to extract the correlation between length and width in a collection or a mixture of anisotropic particles. Compared to the usual statistics on the length associated with a second and independent statistical analysis of the width, this simple plot easily points out the various types of nanoparticles and their (an)isotropy. For each class of nano‐objects, the relationship between width and length (i.e., the strong or weak correlations between these two parameters) may suggest information concerning the nucleation/growth processes. It allows one to follow the effect on the shape and size distribution of physical or chemical processes such as simple ripening. Various electron microscopy pictures from the literature or from the authors′ own syntheses are used as examples to demonstrate the efficiency and simplicity of the proposed 2D plot combined with a multivariate analysis. 相似文献
47.
Modified Lagrangian vortex method with improved boundary conditions for water waves past a thin bottom‐standing barrier 下载免费PDF全文
Herein, the modified Lagrangian vortex method (LVM), a hybrid analytical‐numerical algorithm per se, is devised to simulate the process of vortex formation and shedding from the sharp edge of a zero‐thickness vertical plate under linear water‐wave attack. Application of the Helmholtz decomposition facilitates a convenient switch between the inviscid‐ and viscous‐flow models, thereby enabling easy incorporation of vorticity effects into the potential‐flow calculations for the viscous‐dominated region. In evaluating the potential‐flow component, making good use of the quickly convergent technique with singular basis functions, correctly capturing the singular behavior in velocity fields near the tip of the plate, leads to a considerable reduction of computational burdens and to 12‐decimal‐place accuracy. The viscous correction is carried out via the meshless LVM with improved boundary conditions. Comparisons with previously published results show good agreement. Simulations of vortex generation and evolution illuminate the ability of the present method, and provide a supplement to pertinent experimental works. The hybrid scheme proposed herein allows flexibility for the former LVM and convenience in the code development. Such a compromise fits particularly well for the high‐resolution modeling of sharp‐edged vortex shedding without heavy numerical developments. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
48.
Identification of radical structures on 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5‐dimethylbenzimidazoliumsilver(I)bromide exposed to gamma rays: an EPR study 下载免费PDF全文
Yusuf Ceylan Keziban Usta Ahmet Kunduracioglu Ayhan Usta Bekir Cetinkaya 《Magnetic resonance in chemistry : MRC》2016,54(11):864-869
1‐Pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide and their Ag+ complexes were synthesized and their polycrystal forms were produced by recrystallization in dichloromethane/Et2O solvent system. Structural determinations were carried out by 1H NMR and 13C NMR with a Varian 400 NMR system using tetramethylsilane as internal standard and CDCl3 as solvent. The disappearance of acidic N‐heterocyclic carbene proton showed the formation of Ag(I) complexes. Also, elemental analyses were carried out. Electron paramagnetic resonance (EPR) measurements were performed to determine the formed radical structure on the samples irradiated at the room temperature for 72 h by using 60Co‐source with dose rate of 0.680 kGy. The EPR measurements were carried out in the temperature range of 200 K–450 K. Identical radicals were determined on the irradiated compounds. It was observed that the shapes of the spectra of the samples were independent of the temperature but, the resonance line intensities changed linearly with the temperature. Also, it was detected that the free radical on the 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide is not stable compared to that on the 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
49.
Temperature memory effect and its stability revealed via differential scanning calorimetry in ethylene‐vinyl acetate within glass transition range 下载免费PDF全文
Tao Xi Wang Wei Min Huang Hongmei Chen Rui Xiao Hai Bo Lu Shu Feng Kang 《Journal of Polymer Science.Polymer Physics》2016,54(17):1731-1737
In this article, we reveal the temperature memory effect (TME) in a commercial thermoplastic polymer, namely ethylene‐vinyl acetate (EVA), within its glass transition range via a series of differential scanning calorimeter (DSC) tests. In addition, we investigate the influence of heating holding time and also compare the observed TME in current study with that of shape memory alloys (SMAs). It is concluded that the TME via DSC (without any macroscopic shape change) is achievable within the glass transition range of a polymer. Conversely, although the observed TME shares the many similar features as those in SMAs, due to the nature of micro‐Brownian motion in the glass transition of polymers, the resulted TME is strongly affected by the heating holding time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1731–1737 相似文献
50.