A detailed chemical kinetic model for the supercritical water oxidation of methylamine: The importance of imine formation

A detailed chemical kinetic model has been developed for supercritical water oxidation (SCWO) of methylamine, CH₃NH₂, providing insight into the intermediates and final products formed in this process as well as the dominant reaction pathways. The model was adapted from previous mechanisms, with a revision of the peroxyl radical chemistry to include imine formation, which has recently been identified as the dominant gas-phase pathway in amine oxidation. The developed model can reproduce previous experimental data on methylamine consumption and major product formation to reasonable accuracy, although with deficiencies in describing the induction time. Our simulations indicate that oxidation of the ^•CH₂NH₂ radical to methanimine, CH₂NH, is the major channel in methylamine SCWO, with subsequent hydrolysis of CH₂NH providing the experimentally observed reaction products ammonia and formaldehyde. Integral-averaged reaction rates were used to identify major reaction pathways, and a first-order sensitivity analysis indicated that the concentration of CH₃NH₂ is most sensitive to OH radical kinetics. Overall, this work clarifies the importance of imine chemistry in the oxidation of nitrogen-containing compounds and indicates that they are necessary to model these compounds in SCWO processes.     

Exciton Interactions,Excimer Formation,and [2π+2π] Photodimerization in Nonconjugated Curcuminoid-BF2 Dimers

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF₂ dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional ¹H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.     

Formation of helical beams by use of Pancharatnam-Berry phase optical elements

Spiral phase elements with topological charges based on space-variant Pancharatnam-Berry phase optical elements are presented. Such elements can be achieved by use of continuous computer-generated space-variant subwavelength dielectric gratings. We present a theoretical analysis and experimentally demonstrate spiral geometrical phases for infrared radiation at a wavelength of 10.6microm .     

Path Relinking, Cycle-Based Neighbourhoods and Capacitated Multicommodity Network Design

In this paper, we propose a path relinking procedure for the fixed-charge capacitated multicommodity network design problem. Cycle-based neighbourhoods are used both to move along paths between elite solutions and to generate the elite candidate set by a tabu-like local search procedure. Several variants of the method are implemented and compared. Extensive computational experiments indicate that the path relinking procedure offers excellent results. It systematically outperforms the cycle-based tabu search method in both solution quality and computational effort and offers the best current meta-heuristic for this difficult class of problems.     

Blocks with -power character degrees

Let be a -block of a finite group . If is a -power for all , then is nilpotent.

     

Estimates for Wallis’ ratio and related functions

We present improvements of approximation formula for Wallis ratio related to a class of inequalities stated in [D.-J. Zhao, On a two-sided inequality involving Wallis’s formula, Math. Practice Theory, 34 (2004), 166-168], [Y. Zhao and Q. Wu, Wallis inequality with a parameter, J. Inequal. Pure Appl. Math., 7(2) (2006), Art. 56] and [C. Mortici, Completely monotone functions and the Wallis ratio, Applied Mathematics Letters, 25 (2012), 717-722]. Some sharp inequalities are obtained as a result of monotonicity of some functions involving gamma function.     

A parallel multi-neighborhood cooperative tabu search for capacitated vehicle routing problems

This paper presents a parallel tabu search algorithm that utilizes several different neighborhood structures for solving the capacitated vehicle routing problem. Single neighborhood or neighborhood combinations are encapsulated in tabu search threads and they cooperate through a solution pool for the purpose of exploiting their joint power. The computational experiments on 32 large scale benchmark instances show that the proposed method is highly effective and competitive, providing new best solutions to four instances while the average deviation of all best solutions found from the collective best results reported in the literature is about 0.22%. We are also able to associate the beneficial use of special neighborhoods with some test instance characteristics and uncover some sources of the collective power of multi-neighborhood cooperation.     

On Anosov energy levels of hamiltonians on twisted cotangent bundles

LetT ^* M denote the cotangent bundle of a manifoldM endowed with a twisted symplectic structure [1]. We consider the Hamiltonian flow generated (with respect to that symplectic structure) by a convex HamiltonianH: T ^* M, and we consider a compact regular energy level ofH, on which this flow admits a continuous invariant Lagrangian subbundleE. When dimM3, it is known [9] that such energy level projects onto the whole manifoldM, and thatE is transversal to the vertical subbundle. Here we study the case dimM=2, proving that the projection property still holds, while the transversality property may fail. However, we prove that in the case whenE is the stable or unstable subbundle of an Anosov flow, both properties hold.     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.