The detonation characteristics of methane–oxygen mixtures at pre-detonation pressures of 101–1,013 kPa were investigated in a detonation tube. Both pure methane–oxygen mixtures and mixtures with argon dilution were explored. Measurements made include cell sizes via soot foil, wave speed via high speed ion probes / pressure transducers, and temperature / H2O molar concentration profiles via 100 kHz absorption spectroscopy. Measured cell widths agreed with predicted cell widths based on a ZND length correlation. In addition, the power law fit of cell width with pre-detonation pressure agreed with previous data at less than 101 kPa. Measured detonation wave speeds agreed within 3% of Chapmen-Jouguet for all cases. H2O molar density and temperature were successfully captured up to 507 kPa. However, above 507 kPa pre-detonation pressure, low signal to noise ratio and poor spectral fits at the extreme conditions of the von Neumann spike resulted in unacceptable uncertainty. These results provide a unique dataset to validate kinetics models and high-fidelity computation fluid dynamics codes for methane-oxygen detonations at elevated pre-detonation pressures relevant to rotating detonation rocket engines. 相似文献
Unlike the enchanting yellow‐green flashes of light produced on warm summer evenings by Photinus pyralis, the most common firefly species in North America, the orange lights of Photinus scintillans are infrequently observed. These Photinus species, and likely all bioluminescent beetles, use the same substrates beetle luciferin, ATP and oxygen to produce light. It is the structure of the particular luciferase enzyme that is the key to determining the color of the emitted light. We report here the molecular cloning of the P. scintillans luc gene and the expression and characterization of the corresponding novel recombinant luciferase enzyme. A comparison of the amino acid sequence with that of the highly similar P. pyralis enzyme and subsequent mutagenesis studies revealed that the single conservative amino acid change tyrosine to phenylalanine at position 255 accounted for the entire emission color difference. Additional mutagenesis and crystallographic studies were performed on a H‐bond network, which includes the position 255 residue and five other stringently conserved beetle luciferase residues, that is proximal to the substrate/emitter binding site. The results are interpreted in the context of a speculative proposal that this network is key to the understanding of bioluminescence color determination. 相似文献
Herein, we describe the isolation and characterization of a UnyLinker dimer which, if left uncontrolled, can become incorporated in oligonucleotide products. The dimer is formed as a result of an unusual intermolecular osmium-catalyzed etherification. We demonstrate that by simply replacing H2O2 as the co-oxidant with NMO, none of the UnyLinker dimer impurity is formed. 相似文献
Pure and complete fractions of neodymium, samarium, europium, gadolinium and dysprosium were isolated by means of high performance ion chromatography, using a cation exchange column and gradient elution with alpha-hydroxyisobutyric acid solutions (α-HIBA). Intermediate precision and robustness of the isolation method was investigated, identifying eluent pH as the most important parameter. Investigation of the elution behaviour of the most important fission and activation products and actinides indicated that preventing the accumulation of cesium on the cation exchange column required further isocratic elution with a higher concentrated α-HIBA solution after elution of the lanthanides. A sample matrix free of carbon was achieved by means of acid digestion, followed by UV photo-oxidation, resulting in samples suitable for mass spectrometric analysis.
ABSTRACTWe report the unexpected observation of columnar mesophase formation in a simple 2,7-dibromotetramethoxytriphenylene – by far the most lightly substituted discotic mesogen in this class. This derivative was prepared alongside the 3,6-dibromotriphenylene isomer to demonstrate an alternative, modified synthetic strategy that permits late-stage interchange of alkyl chain substituents. The new method is employed alongside the original route to deliver several new materials, including a conjugated ferrocene–triphenylene–ferrocene triad, a BODIPY–triphenylene–BODIPY triad and a new nematic twin linked through imine bridges. 相似文献
We use the non-oscillatory balanced numerical scheme developed in Part I to track the dynamics of a dry highly nonlinear barotropic/baroclinic
coupled solitary wave, as introduced by Biello and Majda (2004), and of the moisture fronts of Frierson et al. (2004) in the
presence of dry gravity waves, a barotropic trade wind, and the beta effect. It is demonstrated that, for the barotropic/baroclinic
solitary wave, except for a little numerical dissipation, the scheme utilized here preserves total energy despite the strong
interactions and exchange of energy between the baroclinic and barotropic components of the flow. After a short transient
period where the numerical solution stays close to the asymptotic predictions, the flow develops small scale eddies and ultimately
becomes highly turbulent. It is found here that the interaction of a dry gravity wave with a moisture front can either result
in a reflection of a fast moistening front or the pure extinction of the precipitation. The barotropic trade wind stretches
the precipitation patches and increases the lifetime of the moisture fronts which decay naturally by the effects of dissipation
through precipitation while the Coriolis effect makes the moving precipitation patches disappear and appear at other times
and places. 相似文献
Three-dimensional (3D) chemical information was obtained by means of a combination of two-dimensional attenuated total reflection Fourier transform infrared (ATR-FT-IR) imaging with a focal plane array detector and variable angle depth profiling. Since the penetration depth of the evanescent wave in ATR spectroscopy is not limited by diffraction, it was possible to resolve thin sandwiched polymer layers nondestructively within a stack of polymer layers. Chemical images were obtained from layers of different thickness of the laminate by moving a custom-made aperture to specific positions on the condenser lens of the ATR accessory. Sequences of absorption images detect the successive appearance of thin, buried layers of polybutylmethacrylate (d(PBMA) = 400 nm) and polycarbonate (d(TMPC) = 300 nm) in different depths of the stack of polymer layers. The depth resolution of variable-angle ATR-FT-IR imaging is sufficiently high to detect surface roughness at the interface between different polymer layers. Two different stacks of polymers with reordered sandwich-layers were imaged simultaneously, demonstrating the potential of variable angle ATR-FT-IR for 3D-imaging of a sample with xyz-heterogeneity, which can be a powerful analytical technique for materials science and biomedical research. 相似文献
A general synthetic route allowing access to several spirocyclic N-carbethoxy-azabicyclo[3.2.1]octanones is developed. These novel ketones efficiently catalyse alkene epoxidation using Oxone® with up to 91.5% ee. 相似文献
The preparation of 5,7-disubstituted imidazo[5,1-f][1,2,4]triazin-4-amines, exemplified by 5-[3-(benzyloxy)phenyl]-7-cyclobutylimidazo[5,1-f][1,2,4]triazin-4-amine, was developed through a linear and three convergent synthetic strategies, with the latter providing the greatest flexibility for diversification at the 5-position at the last step of the synthesis. 相似文献
We examine a method for computing the change in free energy with temperature of a crystalline solid. In the method, the free-energy difference between nearby temperatures is calculated via overlap-sampling free-energy perturbation with Bennett's optimization. Coupled to this is a harmonically targeted perturbation that displaces the atoms in a manner consistent with the temperature change, such that for a harmonic system, the free-energy difference would be recovered with no error. A series of such perturbations can be assembled to bridge larger gaps in temperature. We test this harmonically targeted temperature perturbation (HTTP) method through the application to the inverse-power soft potential, u(r)=ε(σ/r)(n), over a range of temperatures up to the melting condition. Three exponent values (n=12, 9, and 6) for the potential are studied with different crystal structures, specifically face-centered cubic (fcc), body-centered cubic (bcc), and hexagonal close packing. Absolute free energies (classical only) for each system are obtained by implementing the series to near-zero temperature, where the harmonic model becomes very accurate. The HTTP method is shown to provide very precise results, with errors in the free energy smaller than two parts in 10(5). An analysis of the thermodynamic stability of the various structures in the infinite-system limit confirms previous findings. In particular, for n=12 and 9, the fcc structure is stable for all temperatures up to melting, and for n=6, the bcc crystal becomes stable relative to fcc for temperatures above kT/ε=0.802±0.001. The effects of vacancies and other defects are not considered in the analysis. 相似文献