Effects of OH concentration and temperature on NO emission characteristics of turbulent non-premixed CH4/NH3/air flames in a two-stage gas turbine like combustor at high pressure

This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH₄)/ammonia (NH₃)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH₃ (E_NH3) in CH₄/NH₃ mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH₄/air and NH₃/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH₄/NH₃/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH₃/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH₄ with NH₃. Consequently, NO emissions from CH₄/NH₃ flames were maximized at E_NH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH₄/NH₃ flames increased exponentially with temperature, which was not observed in NH₃/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH₄/NH₃ flames was occurred at a temperature slightly below the maximum temperature, just as in NH₃/air flames. The apparent exponential increase in NO emissions from CH₄/NH₃ flames is attributed to a similar trend in the OH concentration at high temperatures.     

High-temperature protonic motion and low-temperature lattice deformation in one-dimensional hydrogen-bonded molecular chain in tetramethylpyrazine–chloranilic acid (1:1)

Recent theoretical advances have identified several computational algorithms that can be implemented utilizing quantum information processing (QIP), which gives an exponential speedup over the corresponding (known) algorithms on conventional computers. QIP makes use of the counter-intuitive properties of quantum mechanics, such as entanglement and the superposition principle. Unfortunately it has so far been impossible to build a practical QIP system that outperforms conventional computers. Atomic ions confined in an array of interconnected traps represent a potentially scalable approach to QIP. All basic requirements have been experimentally demonstrated in one and two qubit experiments. The remaining task is to scale the system to many qubits while minimizing and correcting errors in the system. While this requires extremely challenging technological improvements, no fundamental roadblocks are currently foreseen.     

Scheduling elective surgery under uncertainty and downstream capacity constraints

The objective of this study is to generate an optimal surgery schedule of elective surgery patients with uncertain surgery operations, which includes uncertainty in surgery durations and the availability of downstream resources such as surgical intensive care unit (SICU) over multi-periods. The stochastic optimization is adapted and the sample average approximation (SAA) method is proposed for obtaining an optimal surgery schedule with respect to minimizing the total cost of patient costs and overtime costs. A computational experiment is presented to evaluate the performance of the proposed method.     

Dienyl homoallyl alcohols via palladium catalyzed ene-type reaction of aldehydes with 1,3-dienes

The combination of Pd catalyst and Xantphos ligand in the presence of Et(3)B nicely promotes the allylation of aldehydes with conjugated dienes to provide dienyl homoallyl alcohols in excellent yields. The reaction occurs selectively at the C-C double bond bearing higher electron density.     

Oxidative dimerization of azoles via copper(II)/silver(I)-catalyzed CH homocoupling

When several azole derivatives such as imidazole, thiazole, and oxazole are treated with a catalyst system of copper(II)/silver(I) under oxygen atmosphere, oxidative dimerization at the CH bond of the 2-position takes place to afford the corresponding bisazoles up to 86% yield.     

meso‐Diketopyripentaphyrin and Diketopyrihexaphyrin as Macrocyclic Tripyrrinone Ligands for NiII Ions

We report expanded porphyrins with pyridine rings and two neighboring carbonyl groups, which allow Ni^II ions to coordinate to the tripyrrinone‐type NNNO coordination structure with Ni?O bonds. The selectivity of tripyrrinone is superior to other pyrrolic or pyridinic cavities of expanded porphyrins. Introduction of α‐carbonyl pyridine next to the tripyrrolic conjugated structure is a powerful strategy for regioselective metalation of flexible expanded porphyrinoids.     

Effect of Alkynyl Group on Reactivity in Photoaffinity Labeling with 2-Thienyl-Substituted α-Ketoamide

Minimalist photo-reactive probes, which consist of a photo-reactive group and a tag for detection of target proteins, are useful tools in chemical biology. Although several diazirine-based and aryl azide-based minimalist probes are available, no keto-based minimalist probe has yet been reported. Here we describe minimalist probes based on a 2-thienyl-substituted α-ketoamide bearing an alkyne group on the thiophene ring. The 3-alkyne probe showed the highest photo-affinity labeling efficiency.     

Large Enhancement of the Single-Molecular Conductance of a Molecular Wire through a Radical Substituent

The single-molecular conductance between two π-conjugated wires with and without a radical substituent has been compared. Specifically, methyl- and iminonitroxide-substituted 4-(biphenyl-4-yl)pyridine wires bound onto a porphyrin template were subjected to scanning tunneling microscopy (STM) apparent-height measurement at the interface between highly oriented pyrolytic graphite (HOPG) and octan-1-oic acid. Statistical analysis of the STM images revealed that the radical-substituted wire has 3.2±1.7-fold higher conductance than the methyl-substituted reference. Although density functional theory (DFT) calculation suggests that only 17 % of the SOMO is distributed on the wire moiety, the effect was significant. This study presents the potential of radical substituents to achieve high conductivity in molecular wires.     

Complex formation of light and heavy lanthanides with DGA and DOODA,and its application to mutual separation in DGA–DOODA extraction system

We studied the stepwise formation constants (β) of water-soluble diglycolamide (DGA) and dioxaoctanediamide (DOODA) for the mutual separation of Ln in a solvent extraction system. TODGA (N,N,N?,N?-tetraoctyl-diglycolamide) and DOODA(C8) (N,N,N?,N?-tetraoctyl-dioxaoctanediamide) exhibit opposite behaviors in extracting both light and heavy Ln through Ln-patterns. Metal complexes of two- and three-folding with water-soluble DOODA and DGA, respectively, were found, and each β value was calculated using distribution ratios. Taking β, their distribution ratio, D, and separation factor, SF, values into consideration, the suitable separation conditions (aqueous phase: 30 mM DOODA(C2) in 1 M HNO₃; organic phase: 0.1 M TODGA in n-dodecane) of multistage extraction (10?×?10 extraction using aqueous and organic phases, including one sample solution) were determined. In this study, La, Pr, and Nd were mainly present in the aqueous phase, whereas Sm–Dy existed in the organic phase. Although these two groups can be easily separated into two phases, the resolution, Rs, values provide for little mutual separation between La–Nd and Sm–Dy under the present conditions.

     

Imaging mass spectrometry of gold nanoparticles in a tissue section as an immunohistochemical staining mass probe

For analysis of low abundance peptides in a tissue section, immunohistochemical staining through antibody‐antigen interaction is a usual technique. The antibody is conjugated with a probe moiety that aids in highly sensitive detection. Gold nanoparticles, which show excellent chemical stability and variation of surface modifications, are expected to act as a sensitive mass probe to desorb gold ions (Au⁺, Au₂⁺, Au₃⁺) that are distinguishable from fragment ions from organic molecules. Here, green fluorescent proteins (GFP) in a tissue section of a transgenic zebrafish were detected by the gold mass probe conjugated with antibodies. Due to the efficient ionization and desorption of gold ions, imaging mass spectrometry of Au₂⁺ ions indicated the distribution of gold nanoparticles stained in a tissue section, and the mass signal distribution was consistent with the area where the GFP‐expressing cells were distributed. Conventional immunofluorescence techniques showed intense autofluorescence that come from intrinsic fluorophores in the tissue section. In contrast, the gold nanoparticles acted as an immunostaining mass probe that displayed significantly lower background signals.