Eulerian and Lagrangian Large-Eddy Simulations of an evaporating two-phase flow

Large-Eddy Simulations (LES) of an evaporating two-phase flow in an experimental burner are performed using two different solvers, CDP from CTR-Stanford and AVBP from CERFACS, on the same grid and for the same operating conditions. Results are evaluated by comparison with experimental data. The CDP code uses a Lagrangian particle tracking method (EL) while the code AVBP can be coupled either with a mesoscopic Eulerian approach (EE) or with a Lagrangian method (EL). After a validation of the purely gaseous flow in the burner, liquid-phase dynamics, droplet dispersion and fuel evaporation are qualitatively and quantitatively evaluated for three two-phase flow simulations. They are respectively referred as: CDP-EL, AVBP-EE and AVBP-EL. The results of the three simulations show reasonable agreement with experiments for the two-phase flow case. To cite this article: J.M. Senoner et al., C. R. Mecanique 337 (2009).     

Detailed analysis of early-stage NOx formation in turbulent pulverized coal combustion with fuel-bound nitrogen

A carrier-phase direct numerical simulation (CP-DNS) of pulverized coal combustion in a mixing layer is performed, considering three NO_x formation mechanisms (fuel-NO_x, thermal-NO_x and prompt-NO_x). Detailed analyses, including reaction path analysis, chemical timescale analysis, and a priori and budget analyses are conducted to investigate the NO_x production mechanisms and the performance of the flamelet model. Considering the high computational cost of CP-DNS, this work focuses on the early phase governed by devolatilization, where char reactions are less important. The reaction path analyses show that the principal thermal-NO reaction contributes to the net consumption of NO in fuel-bound nitrogen pulverized coal flames, which is essentially different from fuel-nitrogen-free flames. The chemical timescale analyses show that the production rates of NO_x species are faster than those of major species, which confirms the suitability of the flamelet tables. The a priori analyses show that the gas temperature and major/intermediate species can be predicted well by the flamelet model, while the NO_x species show significant discrepancies in certain regions. Finally, the budget analyses explain why the flamelet model performs differently for major/intermediate and NO_x species.     

Synthesis of Selectively 15N‐Labeled 2′‐O‐{[(Triisopropylsilyl)oxy]methyl}(=tom)‐Protected Ribonucleoside Phosphoramidites and Their Incorporation into a Bistable 32Mer RNA Sequence

We present optimized reaction conditions for the conversion of 2′‐O‐{[(triisopropylsilyl)oxy]methyl}(=tom) protected uridine and adenosine nucleosides into the corresponding protected (3‐¹⁵N)‐labeled uridine and cytidine and (1‐¹⁵N)‐labeled adenosine and guanosine nucleosides 4, 6, 12 , and 18 , respectively (Schemes 1–4). On a DNA synthesizer, the resulting ¹⁵N‐labeled 2′‐O‐tom‐protected phosphoramidite building blocks 19 – 22 were efficiently incorporated into five selected positions of a bistable 32mer RNA sequence 23 (known to adopt two different structures) (Fig. 1). By 2D‐HSQC and HNN‐COSY experiments in H₂O/D₂O 9 : 1, the ¹⁵N‐signals of all base‐paired ¹⁵N‐labeled nucleotides could be identified and attributed to one of the two coexisting structures of 23 .     

Carbonyl- and carboxyl-substituted enediynes: synthesis, computations, and thermal reactivity

The influence of electron-withdrawing groups (carbonyl and carboxyl) at the alkyne termini on the reactivity of enediynes was investigated by a combination of experimental and computational techniques. While the general chemical reactivity of such enediynes, especially if non-benzannelated, is increased markedly, the thermal cyclization, giving rise to Bergman cyclization products, is changed little relative to the parent enediyne system. This is evident from kinetic measurements and from density functional theory (DFT, BLYP/6-31G + thermal corrections) computations of the experimental systems which show that the Bergman cyclization barriers slightly (3-4 kcal/mol) increase, in contrast to earlier theoretical predictions. The effect on the endothermicities is large (DeltaDeltaH(r) = 7-12 kcal/mol). Hence, the increased reactivity of the substituted enediynes is entirely due to nucleophiles or radicals present in solution. This was demonstrated by quantitative experiments with diethylamine and tetramethyl piperidyl oxide (TEMPO) which both give fulvenes through 5-exo-dig cyclizations.     

Pyranosyl-RNA (‘p-RNA’): NMR and Molecular-Dynamics Study of the Duplex Formed by Self-pairing of Ribopyranosyl-(C-G-A-A-T-T-C-G)

The solution structure of the duplex formed by self-pairing of the p-RNA octamer β-D -ribopyranosyl-(2′→4′)-(CGAATTCG) was studied by NMR techniques and, independently, by molecular-dynamics calculations. The resonances of all non-exchanging protons, H-bearing C-atoms, P-atoms, and of most NH protons were assigned. Dihedral angle and distance constraints derived from coupling constants and NOESY spectra are consistent with a single dominant conformer and corroborate the main structural features predicted by qualitative conformational analysis. The duplex displays Watson-Crick pairing with antiparallel strand orientation. The dihedral angles β and ? in the phosphodiester linkages differ considerably from the idealized values. Model considerations indicate that these deviations from the idealized model allow better interstrand stacking and lessen unfavorable interactions in the backbone. The average base-pair axis forms an angle of ca. 40° with the backbone. The resulting interstrand π-π stacking between either two purines, or a purine and a pyrimidine, but not between two pyrimidines, constitutes a characteristic structural feature of the p-RNA duplex. A 1000-ps molecular-dynamics (MD) calculation with the AMBER force field resulted in an average structure of the same conformation type as derived by NMR. For the backbone torsion angle ?, dynamically averaged coupling constants from the MD calculation agree well with the experimental values, but for the angle β, a systematic difference of ca. 25° remains. The two base pairs at the ends of the duplex are calculated to be highly labile, which is consistent with the high exchange rate of the corresponding imino protons found by NMR.     

Adsorptionsuntersuchungen an Organokieselsäurepolymeren

Adsorption Studies on Organosilic Acid Polymers We present four organosilic acid polymers containing double-4-ring silicate units cross-linked at different degree by different organosilicon bridges. BET surfaces were determined and adsorption isotherms of n-hexane, benzene, nitrogen and water were measured. All polymers are hydrophobic, one of them behaves microporously, the other are unporous. With organic adsorptives, swelling and adsorption occur simultaneously. Possible relations of microporosity and structure are discussed.     

Flamelet LES of a swirl-stabilized multi-stream pulverized coal burner in air and oxy-fuel atmospheres with pollutant formation

A large-eddy simulation of a swirl-stabilized multi-stream laboratory-scale pulverized coal burner designed specifically for oxy-fuel investigation is conducted using a three-mixture-fraction flamelet model, in which both NO_x and SO_x emissions are considered. The simulation results are compared to those in an air atmosphere and the available experimental data. The flame structures and pollutant formation mechanisms are analyzed in detail. The results show that the oxy-coal flame is narrower in the radial direction compared to the air-coal flame. Further, the particle clustering phenomenon can be observed in the oxy-fuel atmosphere. The distributions of the thermo-chemical quantities in different conditions are significantly different. For pollutant formation, the results show that NO is mainly formed around the quarl zone in an oxy-fuel atmosphere, while a large amount of NO is formed in the far downstream region in an air atmosphere. Although the instantaneous distributions of SO_x are qualitatively similar in different conditions, they are quantitatively different due to the different oxygen partial pressure in the air and oxy-fuel atmospheres.     

The two-state issue in the mixed-valence binuclear CuA center in cytochrome C oxidase and N2O reductase

For the CuA site in the protein, sigmau* and piu are the ground and lowest energy excited-states, respectively. EPR data on CuA proteins show a low g parallel value of 2.19 which derives from spin-orbital coupling between sigmau* and piu which requires an energy gap between sigmau* and piu of 3000-4500 cm-1. On the other hand, from paramagnetic NMR studies, it has been observed that the first excited-state is thermally accessible and the energy gap between the ground state and the thermally accessible state is approximately 350 cm-1. This study addressed this apparent discrepancy and evaluated the roles of the two electronic states, sigmau* and piu, in electron transfer (ET) of CuA. The potential energy surface calculations show that both NMR and EPR results are consistent with the electronic/geometric structure of CuA. The anti-Curie behavior observed in paramagnetic NMR studies of CuA results from the thermal equilibrium between the sigmau* and piu states which are at very close energies in their respective equilibrium geometries. Alternatively, the EPR g-value analysis involves the sigmau* ground state in the geometry with a short dCu-Cu where the piu state is a Frank-Condon excited-state with the energy of 3200 cm-1. The protein environment plays a role in maintaining CuA in the sigmau* state as a lowest-energy state with the lowest reorganization energy and high-covalent coupling to the Cys and His ligands for efficient intra- and intermolecular ET with a low-driving force.     

Rieske protein from Thermus thermophilus: 15N NMR titration study demonstrates the role of iron-ligated histidines in the pH dependence of the reduction potential

A unique feature of Rieske proteins is the pH dependence of their reduction potentials. It has been proposed that protonation of the Nepsilon2 atoms of the two histidine rings ligated to the iron-sulfur cluster is coupled with cluster reduction (electron transfer). We have incorporated [15Ndelta1, 15Nepsilon2]-histidine into the Rieske protein from Thermus thermophilis and have used 15N NMR spectroscopy to determine the pKa values of the histidine residues in the oxidized state of the protein. As expected from studies of a Rieske-type ferredoxin, the signals from the 15Ndelta1 atoms directly bound to iron were too broad to be detected, but broad signals could be detected from the 15Nepsilon2 atom of each of the ligated histidine rings. We measured the chemical shifts of these signals as a function of pH between pH 6 and pH 12 and fitted them to theoretical titration curves. The results yielded well-separated pKa values for the two histidines (7.46 and 9.24), with Hill coefficients close to unity. The pKa values are in excellent agreement with values predicted from the pH dependence of the reduction potentials (7.85 and 9.65).