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51.
Hayet Bennadji Lucie Coniglio Francis Billaud Roda Bounaceur Valerie Warth Pierre‐Alexandre Glaude Frédérique Battin‐Leclerc 《国际化学动力学杂志》2011,43(4):204-218
The ignition delay times were measured behind reflected shock waves for temperatures from 1280 to 1930 K, pressures from of 7–9.65 atm, fuel concentrations of 0.4, 0.5, and 1%, and equivalence ratios equal to 0.25, 1.0, and 2.0 in the cases of four unsaturated esters: methyl crotonate, methyl acrylate, ethyl crotonate, and ethyl acrylate. Ignition delay times were measured using chemiluminescence emission from OH at 306 nm and piezoelectric pressure measurements made at the shock tube sidewall. No important difference of reactivity was observed between methyl and ethyl unsaturated esters, methyl and ethyl crotonate having the same reactivity as methyl butanoate. The reactivity of acrylates is greater than that of crotonates especially at the lowest investigated temperatures. Detailed mechanisms for the combustion of the four studied unsaturated esters have been automatically generated using the version of EXGAS software recently improved to take into account this class of oxygenated reactants. These mechanisms have been validated through satisfactory comparison of simulated and experimental results. The main reaction pathways have been derived from flow rate and sensitivity analyses. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 204–218, 2011 相似文献
52.
In cutting plane methods, the question of how to generate the “best possible” set of cuts is both central and crucial. We propose a lexicographic multi-objective cutting plane generation scheme that generates, among all the maximally violated valid inequalities of a given family, an inequality that is undominated and maximally diverse w.r.t. the cuts that were previously found. By optimizing a diversity measure, we introduce a form of coordination between successive cuts. Our focus is on valid inequalities with 0–1 coefficients in the left-hand side and a constant right-hand side, which encompasses several families of valid inequalities. As cut diversity measure, we consider an aggregate of the 1-norm distances w.r.t. the normal vectors of the previous cuts. In this case, our lexicographic multi-objective separation problem reduces to the standard separation problem with different values for the objective function coefficients. The impact of our coordinated cutting plane generation scheme is assessed in a pure cutting plane setting when separating stable set and cut set inequalities for, respectively, the max clique and min Steiner tree problems. Compared to the standard separation of undominated maximally violated cuts, we close the same fraction of the duality gap in a considerably smaller number of rounds and cuts. The potential of our scheme is also indicated by the results obtained in a cut-and-branch setting for max clique, where cut coordination allows for a substantial reduction, on average, of the number of branch-and-bound nodes. 相似文献
53.
Abdullah?M?Asiri Harry?G?Heller David?S?Hughes Michael?B?HursthouseEmail author John?Kendrick Frank?JJ?Leusen Riccardo?Montis 《Chemistry Central journal》2014,8(1):70
Background
Derivatives of fulgides have been shown to have interesting photochromic properties. We have synthesised a number of such derivatives and have found, in some cases, that crystals can be made to change colour on crushing, a phenomenon we have termed “tribochromism”. We have studied a number of derivatives by X-ray crystallography, to see if the colour is linked to molecular structure or crystal packing, or both, and our structural results have been supported by calculation of molecular and lattice energies.Results
A number of 5-dicyanomethylene-4-diphenylmethylene-3-disubstitutedmethylene-tetrahydrofuran-2-one compounds have been prepared and structurally characterised. The compounds are obtained as yellow or dark red crystals, or, in one case, both. In two cases where yellow crystals were obtained, we found that crushing the crystals gave a deep red powder. Structure determinations, including those of the one compound which gave both coloured forms, depending on crystallisation conditions, showed that the yellow crystals contained molecules in which the structure comprised a folded conformation at the diphenylmethylene site, whilst the red crystals contained molecules in a twisted conformation at this site. Lattice energy and molecular conformation energies were calculated for all molecules, and showed that the conformational energy of the molecule in structure IIIa (yellow) is marginally higher, and the conformation thus less stable, than that of the molecule in structure IIIb (red). However, the van der Waals energy for crystal structure IIIa, is slightly stronger than that of structure IIIb – which may be viewed as a hint of a metastable packing preference for IIIa, overcome by the contribution of a more stabilising Coulomb energy to the overall more favourable lattice energy of structure IIIb.Conclusions
Our studies have shown that the crystal colour is correlated with one of two molecular conformations which are different in energy, but that the less stable conformation can be stabilised by its host crystal lattice.54.
C.D. Calvano D. Coniglio P.E. D'Alesio I. Losito T.R.I. Cataldi 《Electrophoresis》2020,41(20):1760-1767
Spirulina microalga (Arthrospira platensis) is an interesting phototrophic organism because of its high content of nutrients including proteins, lipids, essential amino acids, antioxidants, vitamins, polysaccharides, and minerals. Hydrophilic interaction liquid chromatography (HILIC) coupled to linear ion trap (LIT) and Orbitrap Fourier transform mass spectrometry (FTMS) via ESI was employed for the separation and characterization of lipid species in A. platensis. Inositolphosphoceramides (IPC) are minor but important constituents of spirulina; their investigation was accomplished by HILIC–ESI–MS including collision-induced dissociation (MS2, MS3) of deprotonated molecules in the LIT analyzer and a schematic fragmentation pattern is described. All four commercial spirulina samples revealed the occurrence of the same IPC species at m/z 796.6 (d18:0/16:0;1), 810.6 (d18:0/17:0;1), 824.6 (d18:0/18:0;1), and 826.6 (d18:0/17:0;2) but in diverse relative abundance. This study sets the stage for future investigations on IPC in other algae and microalgae. 相似文献
55.
利用螺旋波激发等离子体化学气相沉积(LPP-CVD)技术,以甲烷和氦气为反应气体产生等离子体.通过采集到甲烷的可见光到紫外发射光谱,对甲烷等离子体进行原位诊断,发现存在CH、Ha及Hβ等碎片粒子的光辐射,同时,分析了不同入射功率、气压下CH粒子以及Hβ、Hγ的相对强度变化情况.结果表明:CH粒子的相对强度随着射频功率是先增大而后减小,随工作气压的增大而逐渐减小;随气压及功率的增加,Hβ、Hγ相对强度变化的总体趋势都是先增加而后减小的. 相似文献
56.
We consider the k-Hyperplane Clustering problem where, given a set of m points in Rn, we have to partition the set into k subsets (clusters) and determine a hyperplane for each of them, so as to minimize the sum of the squares of the Euclidean distances between the points and the hyperplane of the corresponding clusters. We give a nonconvex mixed-integer quadratically constrained quadratic programming formulation for the problem. Since even very small-size instances are challenging for state-of-the-art spatial branch-and-bound solvers like Couenne, we propose a heuristic in which many “critical” points are reassigned at each iteration. Such points, which are likely to be ill-assigned in the current solution, are identified using a distance-based criterion and their number is progressively decreased to zero. Our algorithm outperforms the best available one proposed by Bradley and Mangasarian on a set of real-world and structured randomly generated instances. For the largest instances, we obtain an average improvement in the solution quality of 54%. 相似文献
57.
We measure the number Omega(phi) of mechanically stable states of volume fraction phi of a granular assembly under gravity. The granular entropy S(phi)=logOmega(phi) vanishes both at high density, at phi approximately equal to phi_rcp, and a low density, at phi approximately equal to phi_rvlp, where phi_rvlp is a new lower bound we call random very loose pack. phi_rlp is the volume fraction where the entropy is maximal. These findings allow for a clear explanation of compaction experiments and provide the first first-principle definition of the random loose volume fraction. In the context of the statistical mechanics approach to static granular materials, states with phi相似文献
58.
Silvia Coniglio Sandro Colagioia Fabrizio D'Alessandro Valerio D'Elia Valerie Orlando 《Tetrahedron letters》2004,45(28):5375-5378
A new, simple and efficient procedure for the preparation of secondary amides through internal condensation of acylmethanesulfonamides ammonium salts is described. The selective acylation of mixed primary-secondary amines could be an attractive application of the new method. 相似文献
59.
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