Mechanistic aspects of the dehydration and dehydrohalogenation of halo-hydroxyformaldoxime conformers. A quantum chemical model study

A detailed exploration of the configurational and conformational space of chloro- and bromo-hydroxyformaldoximes, Xhfaox (X = Cl, Br) has been carried out with the aid of the B3LYP level of density functional theory, using the 6-31G(d,p) basis set. The most stable configuration in each series of the Clhfaox and Brhfaox conformers corresponds to the Z-s-cis, s-trans configuration, while the highest energy Z-(s-trans, s-cis) conformers were found at 7.0(7.6) and 6.0(6.6) kcal mol(-1), respectively, at the B3LYP(QCISD(T)) levels of theory. Saddle points were also located on the PES of the Clhfaox and Brhfaox compounds corresponding to Z-(s-cis, s-cis) conformers at 13.8(14.9) and 13.6(14.6) kcal mol(-1), respectively, at the B3LYP(QCISD(T)) levels. Upon dehydration Xhfaox could afford a number of isomeric CXNO species. The dehydration processes of Xhfaox are predicted to be endothermic, the computed heats of reactions found in the range of 20.5 to 86.2 kcal mol(-1) and 15.9 to 100.4 kcal mol(-1) at the B3LYP and QCISD(T) levels, respectively. The reaction pathways for the addition of water to halo-fulminates yielding the most stable Xhfaox conformers was predicted to be concerted with a single transition structure, but are asynchronous with activation barriers of 32.8 and 43.0 kcal mol(-1) for the chloro- and bromo-derivatives, respectively. The PES governing the isomerization reactions of the CXNO isomers have also been calculated, and possible isomerization pathways have been delineated. Upon dehydrohalogenation the Xhfaox conformers yield hydroxy-isocyanate or hydroxy-fulminate, the former being more stable by 31.8(18.8) kcal mol(-1) at the B3LYP(QCISD(T)) levels of theory. The reaction pathways for the addition of HX to hydroxy-isocyanate were predicted to be slightly exothermic, the heats of reactions being -3.2 and -5.5 kcal mol(-1), respectively, and have to surmount high activation barriers of 39.7 and 35.0 kcal mol(-1), respectively. Similarly, the addition of HX to hydroxy-fulminate was predicted to be much more exothermic, the heats of reactions being -34.7 and -37.3 kcal mol(-1), respectively, and have to surmount much lower activation barriers of only 10.5 and 7.5 kcal mol(-1) respectively, at the B3LYP level. Finally, calculated structures, relative stability, and bonding properties of all stationary points located on the PES of the systems and reactions studied are thoroughly discussed with respect to computed electronic properties.     

Line profile study with tunable diode laser spectrometers

In this paper, we present the different theoretical line profiles, which can be used to describe a shape of molecular transitions in dilute gases: the Voigt, Galatry, Rautian and speed dependence models. We discuss their limitations and their advantages, and present for illustration different comparisons of model results with experimental data obtained with several diode laser spectrometers suitable for precise line shape measurements.     

Ozone monitoring in a Mediterranean forest using diffusive and continuous sampling

Ambient ozone was measured in a forest in Castelporziano (Italy) characterised by the prevailing presence of Holm-oak trees (Quercus ilex L.) from June to November 2003. Two methods for measuring ozone were used: long-term monitoring using diffusive samplers at three heights within the canopy, and continuous monitoring at two heights using the UV method. Results for one week mean ozone levels above and below the canopy from the diffusive samplers were compared to those obtained using the automatic analyser at the same levels. A good correlation between the two sampling techniques was found. Continuous monitoring showed a daily cycle with a midday maximum and a nocturnal minimum. While the forest floor consistently had the lowest ozone concentration, there were no differences during most daytime hours. The midday maximum is clearly due to downward mixing with O₃-rich air from above. The night-time ozone decay within the canopy is the result of dry deposition of O₃ and most likely due to reaction with biogenically produced NO. AOT40 within and above the canopy mostly exceeded the critical levels.     

A Large Sample Approximation to the Profile Plug-in Upper Confidence Limit

We consider the problem of constructing a 1– upper confidence limit for the scalar parameter ₀ in the presence of the nuisance parameter vector ₀, when the data are discrete. The 'profile plug-in' upper confidence limit is introduced by Kabaila and Lloyd. This confidence limit is based on computing a P-value from an estimator of ₀, replacing the nuisance parameter by the profile maximum likelihood estimate for known, and equating to . Theoretical and numerical evidence for the good coverage properties of this confidence limit is presented by Kabaila and Lloyd. An upper confidence limit should be assessed not only by its coverage properties but also by how large this confidence limit is. We measure how large the profile plug-in upper limit is by using a large sample approximation to it. This large sample approximation is used to delineate further the good properties of this confidence limit.     

Parameters to Define the Electron Beam Trajectory of a Double-Tapered Disc-Loaded Wideband Gyro-TWT in Profiled Magnetic Field

In the method of tapering the cross section of the interaction structure for broadbanding a gyro-TWT, the different portions of the interaction length of the tapered-cross-section waveguide become effective for different frequency ranges if the magnetic field and beam parameters are profiled to maintain the condition of electron cyclotron resonance throughout the interaction length. In the present paper, the study of profiling the magnetic field and beam parameters in steps of the stepped analytical model of a double-tapered disc-loaded circular waveguide was made throughout the steps of the model. In the observed profile, the magnetic flux density in a typical step relative to its value in first-step decreases from first-step (gun-end) to end-step (collector-end) of the model considering the up-tapering schemes, in which structure parameters increase from gun-end to collector-end. Also, the transverse beam velocity in a typical step relative to its value in first-step decreases from gun-end to collector-end. However, the Larmor radius in a typical step relative to its value in first-step as well as the hollow-beam radius in a typical step relative to its value in first-step, both increase from gun-end to collector-end in the model considering the up-tapering schemes.     

基于多孔径闪烁的湍流强度廓线反演方法研究

以多孔径闪烁方法的理论为基础,分别讨论了孔径滤波函数和光谱响应函数对权重函数的影响.根据包括边界层项的Hufnagel-Valley 5/7模型得到的闪烁指数,采用奇异值分解法反演了垂直方向的湍流强度廓线,结果的量级介于10~(-15)~10~(-17)之间,并随高度的增加不断减小,在量级和趋势上与理论模型基本一致;同时结合Shack-Hartman的实际测量结果,反演了水平方向1 km传输路径上的湍流强度分布状况.水平方向反演结果的量级在10~(-14)~10~(-15)之间,随传播距离的变化趋势与实验场地的实际情况较为符合,随时间的变化趋势与合肥地区同期的统计结果基本一致.     

Numerical investigation of the effects of sluice spillway roof profiles on the hydraulic characteristics

There is a need for evolving hydraulically efficient roof profile of bellmouth for high head sluice spillways, as sluice roof is susceptible to cavitation damage. In this paper, formulation and development of a numerical model for simulating the spillway flow and its application to a sluice spillway are presented. The main focus of the simulation study is to apply the developed model to investigate the effects of sluice roof profile geometry on the pressure distribution, the discharge coefficient and the nature of flow regime within the sluice bellmouth. From the analysis of results for eight different roof profiles by varying the entry and exit angles of elliptic bellmouth transition, some important observations have been suggested, which are of practical relevance to hydraulic design engineers. The numerical model results are compared for one profile with physical model study. The simulated results are in close agreement with the measured values. Copyright © 2007 John Wiley & Sons, Ltd.     

Lowest Order Constrained Variational Calculation of Structure Properties of Protoneutron Star

We calculate the structure properties of protoneutron star such as equation of state, maximum mass, radius and temperature profile using the lowest order constrained variational method. We show that the mass and radius of protoneutron star decrease by decreasing both entropy and temperature. For the protoneutron star, it is shown that the temperature is nearly constant in the core and drops rapidly near the crust.     

The Effect of Blood Contained in the Samples on the Metabolomic Profile of Mouse Brain Tissue: A Study by NMR Spectroscopy

(1) Recently, metabolic profiling of the tissue in the native state or extracts of its metabolites has become increasingly important in the field of metabolomics. An important factor, in this case, is the presence of blood in a tissue sample, which can potentially lead to a change in the concentration of tissue metabolites and, as a result, distortion of experimental data and their interpretation. (2) In this paper, the metabolomic profiling based on NMR spectroscopy was performed to determine the effect of blood contained in the studied samples of brain tissue on their metabolomic profile. We used 13 male laboratory CD-1^® IGS mice for this study. The animals were divided into two groups. The first group of animals (n = 7) was subjected to the perfusion procedure, and the second group of animals (n = 6) was not perfused. The brain tissues of the animals were homogenized, and the metabolite fraction was extracted with a water/methanol/chloroform solution. Samples were studied by high-frequency ¹H-NMR spectroscopy with subsequent statistical data analysis. The group comparison was performed with the use of the Student’s test. We identified 36 metabolites in the brain tissue with the use of NMR spectroscopy. (3) For the major set of studied metabolites, no significant differences were found in the brain tissue metabolite concentrations in the native state and after the blood removal procedure. (4) Thus, it was shown that the presence of blood does not have a significant effect on the metabolomic profile of the brain in animals without pathologies.     

Instantaneous phase shifting arrangement for microsurface profiling of flat surfaces

Phase shifting interferometry is a well-established technique for non-contact surface profile measurement. Though phase shifting technique has many advantages, it is marred by a few inaccuracies due to the vibration and mechanical movement of the phase shifter itself. Significant amount of work is reported to theoretically compensate these error sources. But for a few works, prominent achievements have not been reported in eliminating these error sources in phase shifting interferometry. In this paper, a novel optical layout, in combination with instantaneous phase shifting interferometry is described. Experiments were carried out with this setup on a super mirror with a λ/20 surface roughness, to demonstrate the validity of the principle.