Automated multiple development thin-layer chromatography for separation of opiate alkaloids and derivatives

There are three types of opiate alkaloids. First, the poppy alkaloids: morphine, codeine, thebaine, noscapine and papaverine; then, the semi-synthetic and synthetic derivatives used in therapy as antitussives and analgesics, such as pholcodine, ethylmorphine and dextromethorphan; at last narcotic compounds, diacetylmorphine (heroin) and opiates employed as substitutes in treatment of addiction: buprenorphine and methadone. For classical thin-layer chromatography (TLC) of opium alkaloids, it is necessary to use complex eluents with strong alkaline substances to obtain a clean separation between morphinan and isoquinoline compounds. This study purposes the planar chromatographic analysis of these substances by the automated multiple development (AMD) compared with results obtained by classical TLC method. The aim of this work was to achieve the best separation of these opiate alkaloids and derivatives by this modern technique of planar chromatography. The AMD system provided a clean separation for each of three opiates groups studied and the best results have been obtained with universal gradient: methanol 100, methanol-dichloromethane 50/50, dichloromethane 100, dichloromethane 100, hexane 100 for opium alkaloids and with gradient A: 5% of 28% ammonia in methanol 100, acetone 100, acetone 100, ethyl acetate-dichloromethane 50/50, dichloromethane 100 for antitussives and substitutes. Two reagents were used for the detection of alkaloids by spraying: Dragendorff and iodoplatinate reagents. The detection limits with these two reagents were 1 microg for ethylmorphine, thebaine, papaverine, codeine, and 2 microg for morphine and noscapine and other alkaloids.     

A predictive model obtained by identification for the ultrasonic “equivalent” flow velocity at surface vicinity

In the specific applications of surface cleaning and electrochemistry which consist of processes implanting surface irradiation by ultrasound, design of large-scale devices requires us to understand acoustic field distribution together with its quantification. This observation allows systematic measurement of ultrasonic stirring throughout electrochemical determination of “equivalent” flow velocity versus various operating parameters (powers, electrode-horn distances, reactor geometry, frequencies, etc.). A numerical model was proposed to fit our curves and to identify some parameters by taking into account the characteristics of the ultrasonic wave (absorption coefficient, rate of cavitation bubbles and acoustic power). Nevertheless, the flicked behavior of the ultrasonic processes in the vicinity of the electrode as well as bubble presence which induce non-linearities in wave propagation lead us to propose a new approach based on parameter identification by methods currently used in chemical engineering. These parameters were related to physical criteria, and the global model was evaluated throughout analysis of its sensibility criteria.     

Phase controlled superconducting proximity effect probed by tunneling spectroscopy

Using a dual-mode STM-AFM microscope operating below 50 mK we measured the local density of states along small normal wires connected at both ends to superconductors with different phases. We observe that a uniform minigap can develop in the whole normal wire and in the superconductors near the interfaces. The minigap depends periodically on the phase difference. The quasiclassical theory of superconductivity applied to a simplified 1D model geometry accounts well for the data.     

MORMIN: A quasi-Newtonian energy minimizer fitting the nuclear overhauser data

In this article, we describe the program MORMIN, which can simultaneously minimize the mechanical energy of a given macromolecular structure, together with a weighted quadratic penalty function of the difference between the observed and computed nuclear Overhauser effect (nOe) peaks. The gradient of the nOe penalty function relatively to the proton coordinates is computed from an exact closed formula of a matrix exponential derivative. To cut CPU time, the molecular system is partitioned into nonoverlapping subsets containing the protons involved in the observed peaks. The algorithm is no longer exact, but if a 1% relative error is accepted it can be run, on a scalar computer, in about the same CPU time as needed for the calculation of the mechanical energy. We have successfully run the program in more than 1000 situations, including cases where the hybrid method failed because of the occurrence of negative eigenvalues. In some cases, the optimization of the Cartesian coordinates could be successfully extended to individual atomic diffusion times. © 1993 John Wiley & Sons, Inc.     

Erratum to: Energy distribution of electrons in an out-of-equilibrium metallic wire

We have measured with a tunnel probe the energy distribution function of quasiparticles in the middle of a 1.5 μm-long copper wire placed between two reservoirs at different potentials. We find a distribution function close to half the sum of the Fermi distributions in the reservoirs. The deviation from this behavior is not yet understood.     

Spectral characterization in a supersonic beam of neutral chlorophyll a evaporated from spinach leaves

The observation of the light absorption of neutral biomolecules has been made possible by a method implemented for their preparation in the gas phase, in supersonically cooled molecular beams, based upon the work of Focsa et al. [C. Mihesan, M. Ziskind, B. Chazallon, E. Therssen, P. Desgroux, S. Gurlui, and C. Focsa, Appl. Surf. Sci. 253, 1090 (2006)]. The biomolecules diluted in frozen water solutions are entrained in the gas plume of evaporated ice generated by an infrared optical parametric oscillators (OPO) laser tuned close to its maximum of absorption, at ~3 μm. The biomolecules are then picked up in the flux of a supersonic expansion of argon. The method was tested with indole dissolved in water. The excitation spectrum of indole was found cold and large clusters of indole with water were observed up to n = 75. Frozen spinach leaves were examined with the same method to observe the chlorophyll pigments. The Q(y) band of chlorophyll a has been observed in a pump probe experiment. The Q(y) bands of chlorophyll a is centred at 647 nm, shifted by 18 nm from its position in toluene solutions. The ionization threshold could also be determined as 6.1 ± 0.05 eV.     

Multiple Andreev reflections revealed by the energy distribution of quasiparticles

We have performed the tunnel spectroscopy of the energy distribution function of quasiparticles in 5-microm-long silver wires connected to superconducting reservoirs biased at different potentials. The distribution function f(E) presents several steps, which are manifestations of multiple Andreev reflections at the NS interfaces. The rounding of the steps is well explained by electron-electron interactions.     

Density of states in a superconductor carrying a supercurrent

We have measured the tunneling density of states (DOS) in a superconductor carrying a supercurrent or exposed to an external magnetic field. The pair correlations are weakened by the supercurrent, leading to a modification of the DOS and to a reduction of the gap. As predicted by the theory of superconductivity in diffusive metals, we find that this effect is similar to that of an external magnetic field.