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1.
Ketones have been considered as potential biofuels and main components of blend stock for internal engines. To better understand the chemical kinetics of ketones, ignition delay times of 2-pentanone (propyl methyl ketone, PMK) and 3-pentanone (diethyl ketone, DEK) were measured at temperatures of 895–1128 K under 10 and 20 bar, at equivalence ratios (?) of 0.5 and 1.0 in a rapid compression machine (RCM). To explore the impact of carbonyl functionality and resonance stabilized structures of fuel radicals on their combustion kinetics, high-temperature pyrolysis at 1130 K and relatively low-temperature oxidation at 950 K studies were performed in an RCM, and the time-resolved species concentration profiles under these two conditions were quantified using a fast sampling system and gas chromatography (GC). A new kinetic model containing low-temperature reactions was built aiming at predicting the pyrolysis and oxidation behaviors of both ketones. The consumption pathways of the resonance stabilization fuel radicals through oxygen addition and following reactions are promoted since the decomposition rates of these radicals are about 4 orders magnitudes lower than regular fuel radicals. The occurrences of the so-called “addition-dissociation reactions”, i.e., ketones reacting with a hydrogen yielding aldehyde or reacting with a methyl radical yielding shorter-chain-length ketones, are verified in pyrolysis experiments. Based on experiments and model analysis, the carbonyl functionality in both ketones is preserved during the process of β-scissions of fuel radicals and α-scissions of fuel-related acyl radicals, resulting in the direct formation of CO and ketene. However, the position of carbonyl functionality has a significant impact on the species pools.  相似文献   
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Protein‐ligand docking is a commonly used method for lead identification and refinement. While traditional structure‐based docking methods represent the receptor as a rigid body, recent developments have been moving toward the inclusion of protein flexibility. Proteins exist in an interconverting ensemble of conformational states, but effectively and efficiently searching the conformational space available to both the receptor and ligand remains a well‐appreciated computational challenge. To this end, we have developed the Flexible CDOCKER method as an extension of the family of complete docking solutions available within CHARMM. This method integrates atomically detailed side chain flexibility with grid‐based docking methods, maintaining efficiency while allowing the protein and ligand configurations to explore their conformational space simultaneously. This is in contrast to existing approaches that use induced‐fit like sampling, such as Glide or Autodock, where the protein or the ligand space is sampled independently in an iterative fashion. Presented here are developments to the CHARMM docking methodology to incorporate receptor flexibility and improvements to the sampling protocol as demonstrated with re‐docking trials on a subset of the CCDC/Astex set. These developments within CDOCKER achieve docking accuracy competitive with or exceeding the performance of other widely utilized docking programs. © 2015 Wiley Periodicals, Inc.  相似文献   
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We study the Maxwell–Dirac equations in a manifestly gauge invariant presentation using only the spinor bilinear scalar and pseudoscalar densities, and the vector and pseudovector currents, together with their quadratic Fierz relations. The internally produced vector potential is expressed via algebraic manipulation of the Dirac equation, as a rational function of the Fierz bilinears and first derivatives (valid on the support of the scalar density), which allows a gauge invariant vector potential to be defined. This leads to a Fierz bilinear formulation of the Maxwell tensor and of the Maxwell–Dirac equations, without any reference to gauge dependent quantities. We show how demanding invariance of tensor fields under the action of a fixed (but arbitrary) Lie subgroup of the Poincaré group leads to symmetry reduced equations. The procedure is illustrated, and the reduced equations worked out explicitly for standard spherical and cylindrical cases, which are coupled third order nonlinear PDEs. Spherical symmetry necessitates the existence of magnetic monopoles, which do not affect the coupled Maxwell–Dirac system due to magnetic terms cancelling. In this paper we do not take up numerical computations. As a demonstration of the power of our approach, we also work out the symmetry reduced equations for two distinct classes of dimension 4 one-parameter families of Poincaré subgroups, one splitting and one non-splitting. The splitting class yields no solutions, whereas for the non-splitting class we find a family of formal exact solutions in closed form.  相似文献   
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The outwardly propagating spherical flame (OPF) method is popularly used to measure the laminar flame speed (LFS). Recently, great efforts have been devoted to improving the accuracy of the LFS measurement from OPF. In the OPF method, several assumptions are made. For examples, the burned gas is assumed to be static and in chemical equilibrium. However, these assumptions may not be satisfied under certain conditions. Here we consider low-pressure and super-adiabatic propagating spherical flames, for which chemical non-equilibrium exists and the burned gas may not be static. The objective is to assess the chemical non-equilibrium effects on the accuracy of LFS measurement from the OPF method. Numerical simulations considering detailed chemistry and transport are conducted. Stoichiometric methane/air flames at sub-atmospheric pressures and methane/oxygen flames at different equivalence ratios are considered. At low pressures, broad heat release zone is observed and the burned gas cannot quickly reach the adiabatic flame temperature, indicating the existence of chemical non-equilibrium of burned gas. Positive flow in the burned gas is identified and it is shown to become stronger at lower initial pressure. Consequently, the LFS measurement from OPF at low pressures is not accurate if the burned gas is assumed to be static and at chemical equilibrium. For super-adiabatic spherical flames, the burned gas speed is found to be negative due to the local temperature overshoot at the flame front. Such negative speed of burned gas can also reduce the accuracy of LFS measurement. It is recommended that the direct method measuring both flame propagation speed and flow speed of unburned gas should be used to determine the LFS at low pressures or for mixtures with super-adiabatic flame temperature.  相似文献   
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Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.  相似文献   
8.
Pyrrole β-amides are useful building blocks for the preparation of novel molecular architectures that can be used in supramolecular chemistry and sensor development. Under basic conditions, pyrrole β-amides with an α-aldehyde produce different condensation products when reacted with pyrrolinones depending on the amide substitution. Secondary amides form the expected dipyrrinones, but unexpectedly undergo a subsequent trans-amidation with the pyrrolinone nitrogen to produce an unsymmetrical imide (an N-confused fluorescent dipyrrinone). Under the same conditions, tertiary amides produce the expected dipyrrinone carboxylic acids, which have been shown to have strong self-association properties as determined by vapor pressure osmometry measurements, NMR studies, and X-ray crystal structure determination. Furthermore, an N-confused fluorescent dipyrrinone was produced from the same trans-amidation reaction during attempts to decarboxylate a dipyrrinone amide with a 9-carboxylic moiety.  相似文献   
9.
Diisopropyl ether (DIPE) is considered as a promising gasoline additive due to the favorable blending Reid vapor pressure and the low water solubility. To get a good understanding of the DIPE oxidation chemistry, oxidation experiments of a stoichiometric mixture of DIPE/O2/Ar/Kr were performed in a jet-stirred reactor (JSR) at atmospheric pressure over the temperature range of 525–900 K in this work. About 30 intermediates and products were identified and quantified using a photoionization molecular-beam mass spectrometer (PI-MBMS). Furthermore, a detailed kinetic model was proposed for DIPE oxidation, which showed satisfactory performances in predicting the species concentration profiles in this work as well as those in literature. For DIPE oxidation, the fuel consumption was observed only above 750 K, even though DIPE has two tertiary hydrogen atoms that are easy to be abstracted so that low-temperature oxidation reactivity is expected. The low oxidation reactivity at low temperature is because the formed OOQOOH radical mostly dissociates back to QOOH+O2, instead of undergoing intramolecular isomerization which leads to the low-temperature chain-branching. At higher temperature, DIPE is mainly consumed by hydrogen abstraction reactions from the carbon atoms adjacent to the oxygen atom, producing dominantly the IC3H7OC(CH3)2 fuel radical, which then decomposes rapidly via CO bond β-scission instead of combining with O2. In contrast, the minor fuel radical IC3H7OCH(CH3)CH2 tends to go through the O2 addition reaction and the subsequent chain branching reactions, as confirmed by the detection of cyclic ether intermediates. Propylene and acetone are the most abundant intermediates in DIPE oxidation, both of which predominantly come from the initial fuel decomposition steps. Other intermediates are mainly formed via the consumption of these two species.  相似文献   
10.
This study assesses whether the concentrations of biologically important elements in bones are altered by long‐term consumption of cadmium (Cd)‐contaminated water. Heavy metal poisoning has significant impact on humans, and pollutants such as Cd are often found at high concentrations in waterways. Twelve Sprague Dawley rats consumed water with 50 p.p.m. Cd (Cd group), and another 12 consumed normal water (control group). Six subjects from each group were sacrificed after 2 weeks and the others after 4 weeks. Spectra were acquired from the femur by using the EDAX Eagle III micro‐XRF setup, and quantitative calculations were performed by using the fundamental parameter method to determine the concentrations of elements. A bone calcium/phosphorus concentration ratio (Ca/P) of 2.07 ± 0.001 is observed in the spectra from control subjects after 2 weeks and 2.07 ± 0.001 after 4 weeks. In Cd subjects, Ca/P after 2 weeks is 2.04 ± 0.001 and after 4 weeks is 1.97 ± 0.003. Statistically significant differences are obtained when comparing controls with Cd subjects at both time points and when comparing Cd subjects at both time points. Cadmium poisoning significantly affects bone Ca and P concentrations, increasing the likelihood of osteoporosis and other bone diseases. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   
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