The RATIO method for time‐resolved Laue crystallography

A RATIO method for analysis of intensity changes in time‐resolved pump–probe Laue diffraction experiments is described. The method eliminates the need for scaling the data with a wavelength curve representing the spectral distribution of the source and removes the effect of possible anisotropic absorption. It does not require relative scaling of series of frames and removes errors due to all but very short term fluctuations in the synchrotron beam.     

Thermodynamic and spectroscopic properties of Nd:YAG–CO2 Double-Pulse Laser-Induced Iron Plasmas

Double-Pulse Laser-Induced Breakdown Spectroscopy of iron using both Nd:YAG and TEA–CO₂ lasers has been investigated to better understand mechanisms of signal enhancement. The signal dependence on the delay between the two laser pulses shows an enhanced signal when the CO₂ laser pulse interacts with the sample before the Nd:YAG pulse. Signal kinetics and a simple model of sample heating by the CO₂ pulse show that the enhancement during the first 700 ns is due primarily to sample heating. Images of the sample surface after ablation as well as time-integrated pictures of the plasma suggest that particles are ejected from the surface during the first microseconds after the arrival of the CO₂ pulse and provide fuel for the subsequent plasma created by the Nd:YAG laser.     

The lattice of integer partitions and its infinite extension

In this paper, we use a simple discrete dynamical model to study integer partitions and their lattice. The set of reachable configurations of the model, with the order induced by the transition rule defined on it, is the lattice of all partitions of a positive integer, equipped with a dominance ordering. We first explain how this lattice can be constructed by an algorithm in linear time with respect to its size by showing that it has a self-similar structure. Then, we define a natural extension of the model to infinity, which we compare with the Young lattice. Using a self-similar tree, we obtain an encoding of the obtained lattice which makes it possible to enumerate easily and efficiently all the partitions of a given integer. This approach also gives a recursive formula for the number of partitions of an integer, and some informations on special sets of partitions, such as length bounded partitions.     

Determination of diclofenac in pharmaceutical preparations by diffuse reflectance photometry

A quantitative analytical method for the determination of diclofenac in pharmaceutical preparations by diffuse reflectance in the visible region of the spectrum is presented. The color reaction is done directly in the measuring cell immediately after mixing, using small volumes of the analyte solution, of the reagent and of the buffer solutions. All reflectance measurements were carried out in a home made reflectometer equipped with a red LED as light source and a LDR as detector. The calibration curves were constructed from 1.0 to 18 mg mL⁻¹ (about 3.0 × 10⁻³ to 5.5 × 10⁻² mol L⁻¹) of sodium diclofenac or of potassium diclofenac in the analytical solution, with typical correlation coefficients equal to 0.999. The detection limit was estimated to be about 0.7 mg mL⁻¹ (2 × 10⁻³ mol L⁻¹). The method was applied to determine diclofenac in solid and liquid pharmaceutical preparations. The R.S.D. varied from 2% to 4% depending of the sample. The results were compared with those obtained with the HPLC procedure recommended by the United States Pharmacopoeia using the statistical Student's t-test procedure.     

S(N)/S(N)' competition: selective access to new 10-fluoro artemisinins

In this paper, we report a simple route to accede to a new family of C-10 fluorinated derivatives of artemisinin 7. We demonstrated that nucleophilic substitution of the allylic bromide 6 with alcohols can occur at carbon 10 (compounds 7) under solvolytic conditions (S(N)'/S(N) ratio, 87:13). Furthermore, using the particular properties of hexafluoroisopropanol (HFIP), we are able to increase the selectivity of the substitution. Primary alcohols are completely selective for allylic substitution. With amines as nucleophiles, selectivity of substitution is dependent on their nucleophilicity, but attack at carbon 16 was always favored. However, the S(N)'/S(N) ratio could be slightly increased by adding HFIP, which is able to modulate their nucleophilicity through hydrogen bonding. In preliminary in vitro assessments, these new compounds, 7, exhibited a satisfying activity against malaria.     

Structure and charge-state dependence of the gas-phase ionization energy of proteins

Photoionization of protein ions: The ionization energy of polyprotonated protein cations in the gas phase measured using VUV synchrotron radiation appears to be correlated with the charge state z of the protein and its tertiary structure. A simple electrostatic model accounts for the results and also shows predictive capabilities to derive a mean radius R(m) of the protein ion from the ionization energy, and vice versa.     

Improved signal-to-noise ratio in laboratory-based phase contrast tomography

In conventional X-ray microtomography (μCT), the three-dimensional (3D) distribution of the attenuation coefficient of X-rays is measured and reconstructed in a 3D volume. As spatial resolution increases, the refraction of X-rays becomes a significant phenomenon in the imaging process. Although this so-called phase contrast was initially a cumbersome feature in lab-based μCT, special phase retrieval algorithms were developed to exploit these effects. Clear advantages in terms of visualization and analysis can be seen when phase retrieval algorithms are applied, including an increased signal-to-noise ratio. In this work, this is demonstrated both on simulated and measured data.     

Discriminant analysis in the presence of interferences: Combined application of target factor analysis and a Bayesian soft-classifier

A method is described for performing discriminant analysis in the presence of interfering background signal. The method is based on performing target factor analysis on a data set comprised of contributions from analyte(s) and interfering components. A library of data from representative analyte classes is tested for possible contributing factors by performing oblique rotations of the principal factors to obtain the best match, in a least-squares sense, between test and predicted vectors. The degree of match between the test and predicted vectors is measured by the Pearson correlation coefficient, r, and the distribution of r for each class is determined. A Bayesian soft classifier is used to calculate the posterior probability based on the distributions of r for each class, which assist the analyst in assessing the presence of one or more analytes. The method is demonstrated by analyses performed on spectra obtained by laser induced breakdown spectroscopy (LIBS). Single and multiple bullet jacketing transfers to steel and porcelain substrates were analyzed to identify the jacketing materials. Additionally, the metal surrounding bullet holes was analyzed to identify the class of bullet jacketing that passed through a stainless steel plate. Of 36 single sample transfers, the copper jacketed (CJ) and non-jacketed (NJ) class on porcelain had an average posterior probability of the metal deposited on the substrate of 1.0. Metal jacketed (MJ) bullet transfers to steel and porcelain were not detected as successfully. Multiple transfers of CJ/NJ and CJ/MJ on the two substrates resulted in posterior probabilities that reflected the presence of both jacketing materials. The MJ/NJ transfers gave posterior probabilities that reflected the presence of the NJ material, but the MJ component was mistaken for CJ on steel, while non-zero probabilities were obtained for both CJ and MJ on porcelain. Jacketing transfer from a bullet to steel as the projectile passed through the steel also proved difficult to analyze. Over 50% of the samples left insufficient transfer to be identified. Transfer from NJ and CJ jacketing was successfully identified by posterior probabilities greater than 0.8.