Cavitands bearing four fluorophores

The synthesis of novel cavitands containing four fluorophores [tert-butoxycarbonyl protected 2,2′-bis(furyl)benzidine (t-BOC FurylBz) or 5,5′-bis(4-aminophenyl)-2,2′-bifuryl (t-BOC PFDA)] and ionophoric functional groups on the upper rim is reported. The cavitands bearing the four fluorophores emit blue light photoluminescence. In particular, the cavitand containing PFDA moieties exhibits a high photoluminescence quantum yield.     

The slowly reacting mode of combustion of gaseous mixtures in spherical vessels. Part 1: Transient analysis and explosion limits

Frank-Kamenetskii's analysis of thermal explosions is revisited, using also a single-reaction model with an Arrhenius rate having a large activation energy, to describe the transient combustion of initially cold gaseous mixtures enclosed in a spherical vessel with a constant wall temperature. The analysis shows two modes of combustion. There is a flameless slowly reacting mode for low wall temperatures or small vessel sizes, when the temperature rise resulting from the heat released by the reaction is kept small by the heat-conduction losses to the wall, so as not to change significantly the order of magnitude of the reaction rate. In the other mode, the slow reaction rates occur only in an initial ignition stage, which ends abruptly when very large reaction rates cause a temperature runaway, or thermal explosion, at a well-defined ignition time and location, thereby triggering a flame that propagates across the vessel to consume the reactant rapidly. Explosion limits are defined, in agreement with Frank-Kamenetskii's analysis, by the limiting conditions for existence of the slowly reacting mode of combustion. In this mode, a quasi-steady temperature distribution is established after a transient reaction stage with small reactant consumption. Most of the reactant is burnt, with nearly uniform mass fraction, in a subsequent long stage during which the temperature follows a quasi-steady balance between the rates of heat conduction to the wall and of chemical heat release. The changes in the explosion limits caused by the enhanced heat-transfer rates associated with buoyant motion are described in an accompanying paper.     

A modified saddle point method for predicting sound fields above a non-locally reacting porous medium

This paper examines an asymptotic analysis for predicting sound fields above a rigid-frame porous medium, the so-called non-locally reacting porous medium. Their solutions can be represented by a direct wave term, a reflected wave term and a diffraction wave term. Exact and analytical solutions are available for the direct wave and the reflected wave from a perfectly hard ground. In the contrary, the diffraction wave term can only be cast in an integral form that is amenable to approximate analysis. A modified saddle-point method is explored to evaluate the diffraction integral asymptotically. Three different types of non-locally reacting surfaces, which are an extended reaction, a hard-backed layer, and an impedance-backed layer, were considered. The sound fields above these porous surfaces have the same form but they are different by an augmented diffraction term in the solutions. The analytical formula for the total sound fields, which can be stated in a closed form, offer a physically interpretable solution comprising of a direct wave and ground reflected wave terms. This latter term can further be split into a specularly reflected plane wave and ground wave components. A series of numerical comparisons have been conducted to validate the asymptotic analyses presented in this study. It has been demonstrated that the overall sound fields can be predicted well by the formula for all incidence angles and for a wide range of non-locally reacting porous surfaces.     

Fabrication of sulfonated mesoporous carbon by evaporation induced self-assembly/carbonization approach and its supercapacitive properties

Synthesis of functionalized mesoporous carbon by an easy-accessed method is of great importance towards its practical applications.Herein,an evaporation induced self-assembly/carbonization(EISAC) method was developed and applied to the synthesis of sulfonic acid group functionalized mesoporous carbon(SMC).The final mesoporous carbon obtained by EISAC method possesses wormlike mesoporous structure,uniform pore size(3.6 nm),large surface area of 735 m²/g,graphitic pore walls and rich sulfonic acid group.Moreover,the resultant mesoporous carbon achieves a superior electrochemical capacitive performances(216 F/g)to phenolic resin derived mesoporous carbon(OMC,152 F/g)and commercial activated carbon(AC,119 F/g).     

Numerical analysis of conservative unstructured discretisations for low Mach flows

Unstructured meshes allow easily representing complex geometries and to refine in regions of interest without adding control volumes in unnecessary regions. However, numerical schemes used on unstructured grids have to be properly defined in order to minimise numerical errors. An assessment of a low Mach algorithm for laminar and turbulent flows on unstructured meshes using collocated and staggered formulations is presented. For staggered formulations using cell‐centred velocity reconstructions, the standard first‐order method is shown to be inaccurate in low Mach flows on unstructured grids. A recently proposed least squares procedure for incompressible flows is extended to the low Mach regime and shown to significantly improve the behaviour of the algorithm. Regarding collocated discretisations, the odd–even pressure decoupling is handled through a kinetic energy conserving flux interpolation scheme. This approach is shown to efficiently handle variable‐density flows. Besides, different face interpolations schemes for unstructured meshes are analysed. A kinetic energy‐preserving scheme is applied to the momentum equations, namely, the symmetry‐preserving scheme. Furthermore, a new approach to define the far‐neighbouring nodes of the quadratic upstream interpolation for convective kinematics scheme is presented and analysed. The method is suitable for both structured and unstructured grids, either uniform or not. The proposed algorithm and the spatial schemes are assessed against a function reconstruction, a differentially heated cavity and a turbulent self‐igniting diffusion flame. It is shown that the proposed algorithm accurately represents unsteady variable‐density flows. Furthermore, the quadratic upstream interpolation for convective kinematics scheme shows close to second‐order behaviour on unstructured meshes, and the symmetry‐preserving is reliably used in all computations. Copyright © 2016 John Wiley & Sons, Ltd.     

The Kinetic Theory of Simple Reacting Spheres: I. Global Existence Result in a Dilute-Gas Case

Existence of global-in-time, spatially inhomogeneous, and L ¹-renormalized solutions is proven for the model of simple reacting spheres under the assumptions that initially the system has a finite total mass, energy, and entropy.     

Cyclodiphosphazanes with functionalities: Synthesis, reactivity and transition metal chemistry

The saturated, four-membered rings of the type [XP(μ-NR)]₂ containing alternating phosphorus(III) and nitrogen atoms are known as cyclodiphosphazanes or diazadiphosphetidines. The current interest in these well-known heterocycles is due to their catalytic and biological applications besides their excellent synthetic utility as scaffolds to design interesting macrocycles with or without involving main group or transition metals. Although the rigid and nearly-planar neutral P₂N₂ rings resemble [Cu(μ-X)]₂ (X = Cl, Br or I) rhombic units ([Cu(μ-X)]₂ are known for giving a variety of structures with suitable ligands), their utility in designing the high-nuclearity clusters, cages or coordination polymers is scarce. In this context, we fine tuned the coordinating ability of these ligands by incorporating pendant hemi-labile functionalities on phosphorus centers which resulted in the isolation of several interesting molecules. The details are described.     

Speciation of functional groups formed on the surface of ammoxidised carbonaceous materials by XPS method

X-ray photoelectron spectroscopy (XPS) has been used to investigate the fate of nitrogen functional groups present in carbonaceous materials obtained from European plum (Prunus domestica) stones and modified by ammonia-air mixture at 250 or 300 °C. Peaks have been found in the XPS patterns, corresponding to different nitrogen functional forms i.e. pyrrolic, pyridinic, pyridone, amine and chemisorbed nitrogen oxides. It has been found that the distribution of nitrogen functional forms changes as a result of the modification processes.     

L-leap-accelerating the stochastic simulation of chemically reacting systems

Presented here is an L-leap method for accelerating stochastic simulation of well-stirred chemically reacting systems,in which the number of reactions occurring in a reaction channel with the largest propensity function is calculated from the leap condition and the number of reactions occurring in the other reaction channels are generated by using binomial random variables during a leap.The L-leap method can better satisfy the leap condition.Numerical simulation results indicate that the L-leap method can obtain better performance than established methods.     

Exchange of Chemical Species between the Atmospheric Boundary Layer and the Reservoir Layer: An Analytical Interpretation

The exchange of chemical species between the atmospheric boundary layer and the reservoir layer is investigated by means of an analytical solution of the conservation equation of a decaying chemical species. The exchange mechanism is governed by two parameters: the Damköhler number (the ratio of the turbulence time scale to the chemical time scale) and the ratio of a concentration scale in the atmospheric boundary layer to the concentration in the reservoir layer. Depending on the value of these two parameters, the exchange flux between the two layers can vary in sign and by several orders of magnitude. The study demonstrates to what extent chemical transformation determines the transfer of chemical species between the atmospheric boundary layer and the reservoir layer.