Nitric oxide (˙NO) and superoxide (O(2)(-)˙) are ubiquitous in nature. Their reaction product peroxynitrite (ONOO(-)) and notably its conjugated peroxynitrous acid (ONOOH) are highly unstable in aqueous phase. ONOO(-)/ONOOH (referred to as peroxynitrite) isomerize and decompose to NO(3)(-), NO(2)(-) and O(2). Here, we report for the first time GC-MS and HPLC methods for the analysis of peroxynitrite in aqueous solution. For GC-MS analysis peroxynitrite in alkaline solution was derivatized to a pentafluorobenzyl derivative using pentafluorobenzyl bromide. O(15)NOO(-) was synthesized from H(2)O(2) and (15)NO(2)(-) and used as internal standard. HPLC analysis was performed on stationary phases consisting of Nucleosil? 100-5C(18)AB or Nucleodur? C(18) Gravity. The mobile phase consisted of a 10 mM aqueous solution of tetrabutylammonium hydrogen sulfate and had a pH value of 11.5. UV absorbance detection at 300 nm was used. HPLC allows simultaneous analysis of ONOO(-), NO(2)(-) and NO(3)(-). The GC-MS and HPLC methods were used to study stability, synthesis, formation from S-[(15)N]nitrosoglutathione (GS(15)NO) and KO(2), and isomerization/decomposition of peroxynitrite to NO(2)(-) and NO(3)(-) in aqueous buffer. 相似文献
Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C. 相似文献
A new kernel based local linear estimate of the hazard rate, under the random right censorship model is proposed in this article.
We study its finite sample and asymptotic properties and prove its asymptotic normality. Then we bring in three popular methods
for bandwidth selection to the hazard setting as potential bandwidth choice rules for the estimate. We discuss their practical
implementation and through Monte Carlo simulations we use four distributions with different hazard rate shapes to compare
their performance over various sample sizes and levels of censoring. 相似文献
Two types of Equations of State (EoS), which are characterized here as “simple” and “complex” EoS, are evaluated in this study. The “simple” type involves two versions of the Peng–Robinson (PR) EoS: the traditional one that utilizes the experimental critical properties and the acentric factor and the other, referred to as PR-fitted (PR-f), where these parameters are determined by fitting pure compound vapor pressure and saturated liquid volume data. As “complex” EoS in this study are characterized the EoS derived from statistical mechanics considerations and involve the Sanchez–Lacombe (SL) EoS and two versions of the Statistical Associating Fluid Theory (SAFT) EoS, the original and the Perturbed-Chain SAFT (PC-SAFT).
The evaluation of these two types of EoS is carried out with respect to their performance in the prediction and correlation of vapor liquid equilibria in binary and multicomponent mixtures of methane or ethane with alkanes of various degree of asymmetry. It is concluded that for this kind of systems complexity offers no significant advantages over simplicity. Furthermore, the results obtained with the PR-f EoS, especially those for multicomponent systems that are encountered in practice, even with the use of zero binary interaction parameters, indicate that this EoS may become a powerful tool for reservoir fluid phase equilibria modeling. 相似文献
Flame stabilization during non-premixed combustion in curved ducts with a diameter of the order of magnitude of the premixed flame thickness of the reactants was investigated experimentally, since it has been established that this is a configuration with potential advantages in the context of “micro”-combustion. It was shown that, in such “mesoscale” tubes, a stable flame oscillation including extinction/re-ignition phenomena can be established for steady boundary conditions. These oscillations lead, under appropriate conditions, to sound emission in the 50–350 Hz range. This was a mode of stabilization in addition to the “classical” steady flamelet, stabilized through thermal losses to the duct walls at higher values of the Reynolds number. Curvature of the duct was shown to have minimal effect on reactant mixing, which was diffusion-controlled, but significantly affected flame thickness and stabilization. To probe the fuel-oxidizer mixing in the U-shaped, optically accessible tubes, laser induced fluorescence of acetone fuel dopant was used, and the flame structure was studied using OH PLIF. The various stabilization regimes are discussed in terms of the Reynolds and Dean numbers of the tube flow. 相似文献
Using an extensive database of experimental critical properties for heavy compounds, which have been compiled mostly from recent literature sources, it is shown that the ratio Tc: Pc (critical temperature over critical pressure) can be expressed in terms of the van der Waals surface area (Qw), which is readily available for any compound from the group contributions of Bondi (given also in UNIFAC tables). The proposed correlation is based on the hole theory of Kurata and Isida for n-paraffin liquids, which is mathematically equivalent to Flory's theory of polymer solutions. The method is suitable for medium to high molecular weight compounds with unknown critical constants. For example, if only one of the two critical constants is available, then the proposed generalized equation offers a useful rapid procedure for the estimation of the other critical property for use in corresponding states, and other relevant applications where knowledge of the critical properties is required. Furthermore, the Tc: Pc method can be used in many cases for identifying the most suitable among the existing group contribution methods for estimating the critical properties of heavy and complex compounds for which experimental values are, very often, not available. 相似文献