Setting local rank constraints by orthogonal projections for image resolution analysis: Application to the determination of a low dose pharmaceutical compound

Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used.     

Spectral properties of a tight binding Hamiltonian with period doubling potential

We study a one dimensional tight binding hamiltonian with a potential given by the period doubling sequence. We prove that its spectrum is purely singular continuous and supported on a Cantor set of zero Lebesgue measure, for all nonzero values of the potential strength. Moreover, we obtain the exact labelling of all spectral gaps and compute their widths asymptotically for small potential strength.     

Collisional parameters of H2O lines: effects of vibration

A complex semiclassical model for the calculation of line widths and shifts of H₂O broadened by N₂, derived from the Robert and Bonamy approach, is tested by comparisons with measurements for selected transitions in various vibrational bands. The lines retained, which involve rotational states with Kc=J or J−1 have been chosen for two reasons. The first is that they show large variations of the widths with J and thus enable a severe test of the model. The second is that, as explained in this paper, they are well-suited for the study of the effects of vibration on the collisional parameters. The measured values have been extracted from an updated version of a database built years ago (JQSRT 52 (1994) 481) that contains all available measurements. Comparisons between experimental and calculated widths and shifts at room temperature illustrate the quality of the model and clearly demonstrate, for the first time, that there is a vibrational dependence of the broadening. Values of collisional parameters are first studied in fundamental bands. This shows that the theoretical approach accounts for most of the dependence of broadening and shifting on rotational quantum numbers: the variations of γ, which reach a factor of nearly 20 from low to high J values, are correctly accounted for by the model as are some specific features of the shifts δ. Analysis confirms that the bending and stretching vibrations have significantly different effects on δ, due to the vibrational dependence of the intermolecular potential. On the other hand, differences on the widths are rather small with slightly smaller broadening for lines of the bending band. Calculations show that there is a spectroscopic effect, due to the larger rotational constant A in the v₂=1 state. Calculations made for overtone bands involving numerous quanta of the stretching vibration are then presented. They predict that a significant dependence of the width should be observed for high J lines due to the effect of vibration on the interaction potential. This is confirmed by comparisons with measurements for lines involving a change of three and four quanta of stretching vibration.     

Real-time color holographic interferometry devoted to 2D unsteady wake flows

A new optical technique based on real time holographic interferometry in true colors has been implemented around the transonic wind tunnel of the ONERA-Lille center to analyze 2D unsteady wake flows. Tests realized in color interferometry, real time and double exposure, use simultaneously three wavelengths of a continuous waves laser (argon and krypton mixed) and holograms are recorded on silver-halide single-layer panchromatic Slavich PFG03c plates. The very principle of real-time true color holographic interferometry uses three primary wavelengths (red, green and blue) to record, under no-flow conditions, the interference among the three measurement beams and the three reference beams simultaneously on a single reference hologram. After the holographic plate is developed, it is placed on the test setup again in the position it occupied during exposure and the hologram is illuminated again by the three reference beams and three measurement beams. A flat, uniform color can then be observed behind the hologram. So a horizontal, vertical, or even circular fringe pattern can be formed and the achromatic central fringe can be made out very clearly. The single color is used to determine the path difference zero on the interferograms. The flow studied was the unsteady flow downstream of a cylinder placed crosswise in the test section. A sequence of hundred interferograms was recorded on the flow around the cylinder at Mach 0.37. The vortex formation and dissipation phases can be seen very clearly, along with the fringe beat to either side of the cylinder.     

State of the art of color interferometry at ONERA

At ONERA-Lille center a lot of studies have been conducted to characterize complex flows using an optical method based on differential interferometry with Wollaston prism and white polarized light source. Several applications are presented in two-dimensional and axisymmetric flows and in a gaseous mixture where the two gases interface is submitted to acceleration. Then, real-time color holographic interferometry (RCHI) has been developed to obtain the refractive index itself in two dimensional wake flow. The last improvements concern the extension of this method for analyzing three dimensional flows. The authors present a specific setup defined in a single sight direction, the aim being to reproduce the same optical setup along several sight directions, each shifted by a given angle. This optical technique uses reflection holograms where the diffraction efficiency of plates is strongly influenced by the variations in the gelatin thickness produced during the holograms treatment. Problems are discussed and solutions are proposed to control the gelatin shrinkage for two different types of used holograms. The results obtained in a one sight direction make it possible to build in the future an optical setup allowing several simultaneous line-of-sight optical measurements.     

HAC estimation and strong linearity testing in weak ARMA models

In the framework of ARMA models, we consider testing the reliability of the standard asymptotic covariance matrix (ACM) of the least-squares estimator. The standard formula for this ACM is derived under the assumption that the errors are independent and identically distributed, and is in general invalid when the errors are only uncorrelated. The test statistic is based on the difference between a conventional estimator of the ACM of the least-squares estimator of the ARMA coefficients and its robust HAC-type version. The asymptotic distribution of the HAC estimator is established under the null hypothesis of independence, and under a large class of alternatives. The asymptotic distribution of the proposed statistic is shown to be a standard χ² under the null, and a noncentral χ² under the alternatives. The choice of the HAC estimator is discussed through asymptotic power comparisons. The finite sample properties of the test are analyzed via Monte Carlo simulation.     

A short and highly stereoselective synthesis of α-(2-aminothiazolyl)-C-nucleosides

A short route to novel α-(2-aminothiazolyl)-C-nucleosides has been developed. The key step was the high diastereoselective reduction of the hemiacetal intermediates using L-Selectride, which afforded the corresponding R-diols in quantitative yields. These diols were converted, after C4-C1 ring closure and protecting groups cleavage, to their corresponding free α-C-nucleosides.