On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

Chromatography-Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

Design of neutral, mono- or di-cationic water-soluble trihydrazidophosphoradamantanes

The versatile behavior of a trihydrazidophosphoradamantane allowing the synthesis of a variety of neutral, mono- or di-cationic water-soluble molecules of potential interest for biphasic catalysis is reported.     

On the geometry of infinite cyclic subgroups

In this paper we construct an example of a word metric on an infinite cyclic subgroup. This example shows that subexponential distortion does not obstruct non-trivial growth of connected radii. This answers a question of Gromov [6]. The constructed metric has other pathological properies. Specifically, its asymptotic cone depends on the choice of ultrafilter and scaling sequence. The work has been partially supported by the Swiss National Science Foundation.     

IFS attractors and Cantor sets

We build a metric space which is homeomorphic to a Cantor set but cannot be realized as the attractor of an iterated function system. We give also an example of a Cantor set K in R³ such that every homeomorphism f of R³ which preserves K coincides with the identity on K.     

Integral Inequalities and Global Solutions of Semilinear Evolution Equations

A criterion for the nonexplosion of solutions to semilinear evolution equations on Banach spaces is proved. The result is obtained by applying a modification of the Bihari type inequality to the case of a weakly singular nonlinear integral inequality.     

Studies aimed at the synthesis of morphine V an economic approach to (±)-reticuline from 3,4-dihydropapaverine

Regioselective demethylation of 3,4-dihydropapaveraldine ($\text{2}$a) at 7 and 3' positions affords a properly substituted diphenolic key intermidiate ($\text{2}$d) for the synthesis of reticuline and N-norreticuline.     

Asymptotic Analysis of the Current-Voltage Curve of a pnpn Semiconductor Device

We consider the one-dimensional steady-state semiconductor deviceequations modelling a pnpn device. There are two relevant scalingsof the equations corresponding to small and large applied voltages.In both scalings, the semiconductor equations can be consideredas singularly perturbed. It turns out that the small-voltagescaling breaks down for current values between two saturationcurrents. In that interval, the large-voltage scaling has tobe employed. For both scalings, we derive the first-order termsof an asymptotic expansion and show that the reduced problemhas a solution. An example verifies that the current-voltagecurves obtained have the expected qualitative structure.