How effectively bonding evolution theory retrieves and visualizes curly arrows: The cycloaddition reaction of cyclic nitrones

In the present work, the electron density flows involved throughout the progress of the four reaction pathways associated with the intramolecular [3 + 2] cycloaddition of cyclic nitrones Z-1 and E-1 are analyzed using the bonding evolution theory. The present study highlights the nonconcerted nature of the processes, which can be described as taking place in several stages. The first stage consists in the depopulation of the initial CN and CC double bonds to render the N lone pair and the corresponding C N and C C single bonds, and these electronic flows initiate the reactions. The C C and C O sigma bond formations take place later on, once the transition states have been overcome. Along the bridged pathways, the C C bond formation process precedes the O C bond formation event, although, along the fused paths, the O C bond formation process occurs first and the formation of the C C bond is the last electronic flow to take place. Finally, curly arrow representations accounting for the timing of the electron flows are obtained from the bonding evolution theory results.     

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

The molecular mechanism of the reactions between four carbonyl oxides and ammonia/water are investigated using the M06-2X functional together with 6-311++G(d,p) basis set. The analysis of activation and reaction enthalpy shows that the exothermicity of each process increased with the substitution of electron donating substituents (methyl and ethenyl). Along each reaction pathway, two new chemical bonds C−N/C−O and O−H are expected to form. A detailed analysis of the flow of the electron density during their formation have been characterized from the perspective of bonding evolution theory (BET). For all reaction pathways, BET revealed that the process of C−N and O−H bond formation takes place within four structural stability domains (SSD), which can be summarized as follows: the depopulation of V(N) basin with the formation of first C−N bond (appearance of V(C,N) basin), cleavage of N−H bond with the creation of V(N) and V(H) monosynaptic basin, and finally the V(H,O) disynaptic basin related to O−H bond. On the other hand, in the case of water, the cleavage of O−H bond with the formation of V(O) and V(H) basins is the first stage, followed by the formation of the O−H bond as a second stage, and finally the creation of C−O bond.     

Zum schnellen Nachweis von Salicyls?ure in Nahrungsmitteln

Ohne Zusammenfassung     

Kakao

Analytical and Bioanalytical Chemistry -     

The neurotrophin receptor p75NTR mediates early anti-inflammatory effects of estrogen in the forebrain of young adult rats

Background  

Estrogen suppresses microglial activation and extravasation of circulating monocytes in young animals, supporting an anti-inflammatory role for this hormone. However, the mechanisms underlying estrogen's anti-inflammatory effects, especially in vivo, are not well understood. The present study tests the hypothesis that anti-inflammatory effects of estrogen are mediated by the pan-neurotrophin receptor p75NTR. Previously, we reported that estrogen attenuated local increases of interleukin(IL)-1β in the NMDA-lesioned olfactory bulb, while further increasing NGF expression.     

A rapid technique for synthesis of metallic nanoparticles for surface enhanced Raman spectroscopy

Incubator‐shaker method was used as a rapid technique to fabricate an efficient surface enhanced Raman scattering (SERS) substrate by combination of zero valent nanostructures and carbon fiber, which shows dramatic Raman enhancement of nitroaromatic molecule. The fabricated Ag nanoparticle on carbon‐fiber substrate (Ag–C) was used as an efficient SERS substrate to detect the adsorbed 2, 4‐dinitrotoluene molecules with a detection limit of 50 ppm. In advent, our developed SERS substrates could have great potential in detecting other nitro‐aromatic based‐explosive materials, such as 2, 4, 6‐trinitrotoluene molecules. Copyright © 2013 John Wiley & Sons, Ltd.     

电子、正电子、离子等离子体尾场中被加速正电子的研究

为了研究在激光驱动的等离子体尾场中被加速正电子的动力学,使用了由电子、正电子、离子组成的等离子体,通过采用数值模拟方法得到了非对称脉冲驱动的尾波场中被加速的正电子的运动相图、动能变化,势能。数据结果表明：非对称激光脉冲驱动尾场中正电子得到很高的能量。提高等离子体中的正电子比例会使电子和正电子的加速效果减弱。在非对称激光脉冲驱动的激光尾场中,为了有效地加速正电子,要选择恰当的上升激光脉冲长度和下降激光脉冲长度。     

Analysis of complex oscillatory dynamics of a pH oscillator

Reaction systems that display pronounced periodic and aperiodic variations in the pH value of the reaction medium are known as pH oscillators. A member of this family of reactions studied here, the Cu(II)-catalyzed oxidation of thiosulfate by hydrogen peroxide in acidic solution, is known to display a rich variety of oscillatory dynamics. We focus on experimental time series showing complex aperiodic dynamics that simultaneously possesses the characteristics of period-doubled large-amplitude oscillations and irregular small-amplitude oscillations reminiscent of mixed-mode dynamics. An analysis based on the reconstruction of the attractor from the measured time series by two different methods and subsequent calculation of the maximal Lyapunov exponent reveals that this interesting dynamical regime is a manifestation of deterministic chaos. The text was submitted by the authors in English.     

Attenuation of sound in wide ducts with flow at elevated pressure and temperature

At ambient conditions the acoustic losses within the fluid are two orders of magnitude smaller than those occurring at a duct wall, so that they are commonly neglected in duct acoustics. Recent measurements revealed an increasing sound attenuation at elevated pressure and temperature, which cannot be justified by the viscothermal losses at the wall alone. In the first part, this paper compiles available models to pursue a comprehensive treatment of the sound attenuation in a duct at elevated pressure and temperature. The second part presents an experimental study of the attenuation. The measurements have been performed at the Hot Acoustic Test Rig, where pressure and temperature can be independently adjusted from their ambient values up to 1100 kPa and 823 K, respectively. The theoretical prediction of the total losses matches the experimental data, thus confirming that the losses within the fluid cannot be neglected in ducts at elevated pressure and temperature.