Endor and eseem study of the radical obtained by γ irradiation of a single crystal of ammonium tartrate

The radical obtained by γ irradiation of a single crystal of ammonium tartrate has been identified by paramagnetic resonance spectroscopies. The proton hyperfine coupling tensors have been obtained, from the angular dependence of the ENDOR transition frequencies. ESEEM spectra of the radical have been also obtained. The intensities of the ESEEM lines are related to the depth of the modulation, which has a dramatic angular dependence.     

On equality in an upper bound for the restrained and total domination numbers of a graph

Let G=(V,E) be a graph. A set S⊆V is a restrained dominating set (RDS) if every vertex not in S is adjacent to a vertex in S and to a vertex in V?S. The restrained domination number of G, denoted by γ_r(G), is the minimum cardinality of an RDS of G. A set S⊆V is a total dominating set (TDS) if every vertex in V is adjacent to a vertex in S. The total domination number of a graph G without isolated vertices, denoted by γ_t(G), is the minimum cardinality of a TDS of G.Let δ and Δ denote the minimum and maximum degrees, respectively, in G. If G is a graph of order n with δ?2, then it is shown that γ_r(G)?n-Δ, and we characterize the connected graphs with δ?2 achieving this bound that have no 3-cycle as well as those connected graphs with δ?2 that have neither a 3-cycle nor a 5-cycle. Cockayne et al. [Total domination in graphs, Networks 10 (1980) 211-219] showed that if G is a connected graph of order n?3 and Δ?n-2, then γ_t(G)?n-Δ. We further characterize the connected graphs G of order n?3 with Δ?n-2 that have no 3-cycle and achieve γ_t(G)=n-Δ.     

Ignition delay measurements of four component model gasolines exploring the impacts of biofuels and aromatics

This study explores the impacts of combinations of biofuel (ethanol, isobutanol and 2-methyl furan) and aromatic (toluene) compounds in a four component fuel blend, at fixed research octane number (RON) on ignition delay measured in an advanced fuel ignition delay analyzer (AFIDA 2805). Ignition delay measurements were performed over a range of temperatures from 400 to 725 °C (673 to 998 K) and two chamber pressures of 10 and 20 bar. The four component mixtures are compared to primary reference fuels at RON values of 90 and 100. The ignition delay measurements show that as the aromatic and biofuel concentrations increased, two stage ignition behavior was suppressed, at both initial chamber pressures. But both RON 100 (isooctane) and RON 90 reference fuels showed two stage ignition behavior, as did fuel mixtures with low biofuel and aromatic content. RON 90 fuels showed stronger two stage ignition behavior than RON 100 fuels, as expected. Depending on the type of biofuel in the mixture, the ignition delay at low chamber temperatures could be far greater than for the reference fuels. In particular, for the RON 100 mixtures at either 10 or 20 bar initial chamber pressure, the ignition delay at 400 °C (673 K) for the high level blend of 2-methyl furan and toluene (30 vol% of each) exhibited an ignition delay that was 10 times longer than for neat isooctane. The results show the strong non-linear octane blending response of these three biofuel compounds, especially in concert with the kinetic antagonism that toluene is known to display in mixtures with isooctane. These results have implications for the formulation of biofuel mixtures for spark ignition and advanced compression ignition engines, where this non-linear octane blending response could be exploited to improve knock resistance, or modulate the autoignition process.     

The One-Shot Method in SU2

For PDE-constrained optimization tasks the one-shot approach is well-suited. The solution of the state equation is augmented with an adjoint solver to provide approximate reduced derivatives that can be used in an optimization iteration to change the design. In this paper different one-shot strategies for SU2 are implemented and tested for aerodynamic shape optimization in the open-source multi-physics package SU2 to extend the choice of optimization algorithms. These include the application of the one-shot approach when considering additional constraints apart from the state equation. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A comparison of direct thermal desorption with solvent extraction for gas chromatography-mass spectrometry analysis of semivolatile organic compounds in diesel particulate matter

Direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS) is a technique that is finding application in the characterisation of the semivolatile organic carbon fraction of ambient and combustion source particulate matter (PM) collected on filters. In this study, three DTD-GC-MS methods were assessed and compared to a conventional solvent extraction method for analysis of a mixture of target analytes in solution and of diesel PM collected on quartz filters. The target analytes included n-alkanes, hopanes, steranes and polycyclic aromatic hydrocarbons. This study showed that while the three DTD-GC-MS methods were generally comparable to the solvent extraction method, (1) the choice of calibration strategy and calibration materials has a significant impact on the measured accuracy of a method; (2) very large variations were seen in all methods for the more volatile compounds such as C₁₀ to C₁₃ n-alkanes and naphthalene; (3) accuracy, defined as difference from the known concentration of a liquid sample, ranged from 5% to 32%; (4) precision, defined as the relative standard deviation, ranged from 4% to 16%. The average difference of DTD-GC-MS results from the solvent extraction results for the diesel PM filters ranged from 20% to 40%. This difference was driven by the large number of target analytes present at relatively low concentrations (<25 pg/mm²) and their corresponding higher variability. Differences in performance among the compound classes were noted. Minimum detection limits for the DTD-GC-MS methods were on the order of 0.1 to 1 pg/mm² and were as good as or better than those obtained for the solvent extraction method.     

Novel Copolymers of Styrene. 7. Chlorine Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel trisubstituted ethylenes, chlorine ring-substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₃CH?C(CN)CONH₂ (where R is 2,3-dichloro, 2,4-dichloro, 2,6-dichloro, 3,4-dichloro, 2-chloro-5-nitro, 4-chloro-3-nitro, 5-chloro-2-nitro) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution in the presence of a radical initiation (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. Thus, the order of relative reactivity (1/r1) and the tendency toward alternation of monomer units in the copolymer for the monomers is 2-Cl-5-NO₂ (3.09) > 5-Cl-2-NO₂ (1.88) > 4-Cl-3-NO₂ (0.97) > 2,6-Cl₂ (0.93) > 3,4-Cl₂ (0.31) > 2,4-Cl₂ (0.30) > 2,3-Cl₂ (0.22). High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3.5–5.0 wt%), which then decomposed in the 500–800°C range.     

Visible-Light Cascade Photooxygenation of Tetrahydrocarbazoles and Cyclohepta[b]indoles: Access to C,N-Diacyliminium Ions

Tetrahydrocarbazoles and perhydrocyclohepta[b]indoles undergo a catalytic cascade singlet oxygenation in alkaline medium, which leads to chiral tricyclic perhydropyrido- and perhydroazepino[1,2-a]indoles in a single operation. These photooxygenation products are new synthetic equivalents of uncommon C,N-diacyliminium ions and can be functionalized with the aid of phosphoric acid organocatalysis.