Quantum-chemical study on the catalytic activity of TinRumO2(1 1 0) surfaces on chlorine evolution

Based on the generalized gradient approximation (GGA), Perdew-Wang-91 (PW91) combined with a periodic slab model has been applied to study the catalytic activity of chlorine evolution on TinRumO2(1 1 0) surface. Metal oxide model TinRumO2 has been established with pure TiO2 and RuO2 on the basis set of Double Numerical plus polarization (DNP), in which the proportion of n:m was 3:1, 1:1, or 1:3. Analysis on the reaction activity in the electrochemical reaction and the electrochemical desorption reaction was based on Frontiermolecular orbital theory. The results show that the TinRumO2 with a ratio of Ti:Ru at 3:1 is best facilitates the electrochemical reaction and electrochemical desorption reaction to produce M-Clads intermediate and precipitate Cl2. In addition, the adsorption energy of Cl on the surface of Ti3Ru1O2 possesses the minimum value of 2.514 eV, and thus electrochemical desorption reaction could occur most easily.     

Tetrabenzoperipentacene: Stable Five‐Electron Donating Ability and a Discrete Triple‐Layered β‐Graphite Form in the Solid State

An oxidative ring‐closure reaction of a tetranaphthylpyrene derivative led to the synthesis of a 56 all‐carbon conjugated tetrabenzoperipentacene. In the single‐crystal X‐ray structure, three molecules make a triple‐layered cluster by π‐stacking, wherein each layer rotates by 120°, and is thus considered a petit β‐graphite. As for the optical properties, the Stokes shift is extremely small (10 cm^?1), thus indicating its remarkably rigid framework. The tetrabenzoperipentacene exhibits reversible five‐electron oxidation waves in cyclic voltammetry, and is regarded as a counterpart to the fullerene C₆₀ in terms of stable multicharge‐storage nanocarbon materials.     

Synthesis of Extended π‐Systems through C–H Activation

Activation of aromatic C? H bonds by a transition metal catalyst has received significant attention in the synthetic chemistry community. In recent years, rapid and site‐selective extension of π‐electron systems by C–H activation has emerged as an ideal methodology for preparing organic materials with extended π‐systems. This Review focuses on recently reported π‐extending C–H activation reactions directed toward new optoelectronic conjugated materials.     

meso‐Dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Unusual cis Tautomeric Form

meso‐Monobenzoporphycene (mMBPc) and meso‐dibenzoporphycene (mDBPc), in which one or two benzene moieties are fused at ethylene‐bridged positions (meso‐positions) of porphycene, were prepared in an effort to further delocalize the π‐electrons within the porphycene molecule. mMBPc and mDBPc were fully characterized by mass spectrometry, ¹H and ¹³C NMR spectroscopy, and X‐ray crystallography. The longest‐wavelength Q‐bands of mMBPc and mDBPc are red‐shifted by 92 nm and 418 nm, respectively, compared to that of the unsubstituted porphycene (Pc). Electrochemical measurements indicate that the HOMO is destabilized and the LUMO is stabilized by the fused benzene moieties at the meso positions. Furthermore, both XPS and theoretical studies support the presence of a cis tautomeric form in the ground state of mDBPc, despite the fact that essentially all known porphycene derivatives adopt the trans tautomeric form.     

Organic Crystals with Near‐Infrared Amplified Spontaneous Emissions Based on 2′‐Hydroxychalcone Derivatives: Subtle Structure Modification but Great Property Change

A series of highly efficient deep red to near‐infrared (NIR) emissive organic crystals 1 – 3 based on the structurally simple 2′‐hydroxychalcone derivatives were synthesized through a simple one‐step condensation reaction. Crystal 1 displays the highest quantum yield (Φ_f) of 0.32 among the reported organic single crystals with an emission maximum (λ_em) over 710 nm. Comparison between the bright emissive crystals 1 – 3 and the nearly nonluminous compounds 4 – 7 clearly gives evidence that a subtle structure modification can arouse great property changes, which is instructive in designing new high‐efficiency organic luminescent materials. Notably, crystals 1 – 3 exhibit amplified spontaneous emissions (ASE) with extremely low thresholds. Thus, organic deep red to NIR emissive crystals with very high Φ_f have been obtained and are found to display the first example of NIR fluorescent crystal ASE.     

Self‐Assembly and Disassembly of Vesicles as Controlled by Anion–π Interactions

Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self‐assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self‐assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self‐assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO₃^?, Cl^?, and Br^?, or by changing the pH value of the medium.     

Hyperbolicity of Steady‐State Equations of Gas Shear Flows in a Thin Layer

The steady08931n7q155618/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">state three08931n7q155618/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">dimensional motion of an ideal gas in a thin layer of variable height is considered. In the long08931n7q155618/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">wave approximation, the equations of gas dynamics reduce to a system of integrodifferential equations. The generalized characteristics and hyperbolicity conditions of the obtained system are found.     

The modified Casson＇s equation and its application to pipe flows of shear-thickening fluid

A few additional data from our previous experiments were plotted to emphasize the shear-thickening behavior of deoxy sickle erythrocyte (SS) suspension. A constitutive equation (named as FX equation) was developed and applied to a cylindrical pipe flow of a shear-thickening fluid. A blunt velocity profile and its volume flow rate were calculated. The flow was non-viscous (potential) in the central part of the pipe (i.e. the central core or the central plug-flow), and became more and more viscous towards the wall of the pipe after a specific radial distance, which was determined by a critical shear rate of 03g35191337m0/MediaObjects/s10409-005-0038-6flb1.gif" alt="MediaObjects/s10409-005-0038-6flb1.gif" align="middle"> (named as Fung03g35191337m0/xxlarge8217.gif" alt="rsquo" align="BASELINE" BORDER="0">s shear rate). Furthermore, combining the FX equation with the original Casson03g35191337m0/xxlarge8217.gif" alt="rsquo" align="BASELINE" BORDER="0">s equation, the author obtained a modified Casson03g35191337m0/xxlarge8217.gif" alt="rsquo" align="BASELINE" BORDER="0">s equation by introducing 03g35191337m0/MediaObjects/s10409-005-0038-6flb1.gif" alt="MediaObjects/s10409-005-0038-6flb1.gif" align="middle">.The English text was polished by Yunming Chen.     

Effect of Free‐Stream Turbulence on the Flow Structure near a Wedge and the Windward Side of an Airfoil

The flow structure behind wire grids is studied for flows with a low subsonic velocity, and the effect of grids on the boundary0172557471/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">layer flow structure is considered. It is shown that the mean0172557471/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">velocity inhomogeneity induced by the grid does not disappear until a distance of 925 calibers downstream of the grid is reached. Liquid0172557471/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">crystal thermography combined with hot0172557471/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">wire measurements made it possible to find the source of steady large0172557471/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">scale streamwise vortex structures in the boundary layer on a wedge and on an airfoil and to determine the parameters of these structures.