Photoacoustic spectroscopy with quantum cascade distributed-feedback lasers

We present photoacoustic (PA) spectroscopy measurements of carbon dioxide, methanol, and ammonia. The light source for the excitation was a single-mode quantum cascade distributed-feedback laser, which was operated in pulsed mode at moderate duty cycle and slightly below room temperature. Temperature tuning resulted in a typical wavelength range of 3cm(-1)at a linewidth of 0.2cm(-1). The setup was based on a Herriott multipass arrangement around the PA cell; the cell was equipped with a radial 16-microphone array to increase sensitivity. Despite the relatively small average laser power, the ammonia detection limit was 300 parts in 10(9)by volume.     

Computational and experimental investigation of flow over a transient pitching hydrofoil

The present study is developed within the framework of marine structure design operating in transient regimes. It deals with an experimental and numerical investigation of the time–space distribution of the wall-pressure field on a NACA66 hydrofoil undergoing a transient up-and-down pitching motion from 0° to 15° at four pitching velocities and a Reynolds number Re = 0.75 × 10⁶. The experimental investigation is performed using an array of wall-pressure transducers located on the suction side and by means of time–frequency analysis and Empirical Modal Decomposition method. The numerical study is conducted for the same flow conditions. It is based on a 2D RANS code including mesh reconstruction and an ALE formulation in order to take into account the foil rotation and the tunnel walls. Due to the moderate Reynolds number, a laminar to turbulent transition model was also activated. For the operating flow conditions of the study, experimental and numerical flow analysis revealed that the flow experiences complex boundary layer events as leading-edge laminar separation bubble, laminar to turbulent transition, trailing-edge separation and flow detachment at stall. Although the flow is relatively complex, the calculated wall pressure shows a quite good agreement with the experiment provided that the mesh resolution and the temporal discretization are carefully selected depending on the pitching velocity. It is particularly shown that the general trend of the wall pressure (low frequency) is rather well predicted for the four pitching velocities with for instance a net inflection of the wall pressure when transition occurs. The inflection zone is reduced as the pitching velocity increases and tends to disappear for the highest pitching velocity. Conversely, high frequency wall-pressure fluctuations observed experimentally are not captured by the RANS model. Based on the good agreement with experiment, the model is then used to investigate the effects of the pitching velocity on boundary layer events and on hydrodynamic loadings. It is shown that increasing the pitching velocity tends to delay the laminar-to-turbulence transition and even to suppress it for the highest pitching velocity during the pitch-up motion. It induces also an increase of the stall angle (compared to quasi-static one) and an increase of the hysteresis effect during pitch-down motion resulting to a significant increase of the hydrodynamic loading.     

Investigation and optimisation of a multipass resonant photoacoustic cell at high absorption levels

A theoretical and experimental investigation of photoacoustic (PA) signals in a resonant multipass PA cell with high background absorption (up to 29 m^-1) is presented. An analogous electric transmission line model including discontinuity inductances at cross section changes was used to model the first longitudinal acoustic mode of the multipass PA cell equipped with two buffer volumes. This model was validated with experimentally obtained results and used to predict the behaviour of the PA cell for different multipass arrangements and different buffer volume diameters. The highest PA signal is obtained for high pass number and large buffer radius. Increasing the absorption coefficient of the medium enhances the PA signal until a maximum is reached, leading to a minimum for the PA signal sensitivity. For a given background absorption, the number of passes required to maximise the sensitivity depends on the absorption coefficient. The model allows the determination of the best-suited number of passes for a given absorption coefficient and cell geometry. PACS 82.80.Kd; 42.62.Fi; 82.80.Gk     

Etude de l'absorption optique du vanadium en couches minces interpretation par la theorie des bandes d'energie

Optical absorption of vanadium thin films has been determinated from 0.32 to 5.5 eV from reflectance and transmittance data. The films have been deposited in ultra high vacuum and the measurements have been realised in situ. Between 1 to 5.5 eV, we note a large absorption band which is independant of the photons angle of incidence and polarisation; with an important maximum and a shoulder respectively at 3.1 and 2 eV. We explain this absorption band by direct interband transitions deduced from theorical bands calculated by Yasui et al. From 0.32 to 1 eV, the observed absorption is principally due to intraband transitions.     

抗坏血酸有机锗倍半氧化物的合成及抗癌活性研究

通过三氯锗仿与抗坏血酸分子的加成反应,合成了一种新型有机锗倍半氧化物,产物的结构通过元素分析、IR及UV光谱等方法进行了表征．生物活性实验表明合成物对小鼠S-180肿瘤生长具有显著的抑制作用．     

Determining the effect of Ru substitution on the thermal stability of CeFe4−xRuxSb12

The ternary, rare-earth filled (RE) Skutterudites (REM₄Pn₁₂; M = Fe–Os; Pn = P–Sb) have been proposed for use in high-temperature thermoelectric devices to convert waste heat to useful power. CeFe₄Sb₁₂ has been one of the most popular materials proposed for this application; however, it oxidizes at relatively low temperatures. The thermal stability of Skutterudites can be enhanced by selective substitution of the constituent elements and Eu(Fe,Ru)₄Sb₁₂ variants have been found to oxidize at temperatures above that of CeFe₄Sb₁₂. Unfortunately, these materials have poor thermoelectric properties. In this study, the thermal stability of CeFe_4−xRu_xSb₁₂ was examined depending on the value of x. (These compounds have similar thermoelectric properties to those of CeFe₄Sb₁₂.) It has been found by use of TGA and XANES that the temperature at which point CeFe_4−xRu_xSb₁₂ oxidizes increases with greater Ru substitution. XANES was also used to confirm the general charge assignment of Ce³⁺Fe_4−x²⁺Ru_x²⁺Sb₁₂¹⁻.     

Routine analysis by high precision gas chromatography/mass selective detector/isotope ratio mass spectrometry to 0.1 parts per mil

Stable isotope methods are potentially quite useful for validating natural or enhanced mineral degradation of contaminants. For this reason, a continuous flow gas chromatograph (GC), isotope ratio mass spectrometer (IRMS) has been coupled with a quadrupole mass selective detector (MSD) to allow simultaneous mass spectral and stable carbon isotope ratio data to be obtained from a single chromatographic analysis. This allows the target contaminant and any extra-cellular degradation intermediates to be both qualified and quantified. Previously acceptable limits of precision (0.3 parts per mil) are undesirable given the small fractionation observed during aerobic degradation. To further understand the fate of organic contaminants and to gain information about the metabolic degradative pathway employed by a microorganism, routine isotopic analyses on a range of analytes have been performed. Quantities of sample producing mass-44 ion beam signal (I(44)) of 2 x 10(-10) to 1 x 10(-8) A were analysed. When the IRMS was tuned for high sensitivity, ion source nonlinearities were overcome by peak height correction from an algorithm that was produced using known isotopic standards of varying concentrations. This led to sample accuracy of <0.01 per thousand and sample precision of 0.1 per thousand. Copyright 1999 John Wiley & Sons, Ltd.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.