High-dynamic-range laser-pulse-contrast measurement with a plasma-shuttered streak camera

The dynamic range of a picosecond visible streak camera has been improved by the combination of a plasma shutter and multishot averaging performed with a photoconductive switch sweep circuit. We use this technique to measure the contrast of a 100-fs laser pulse over 2 ns with a dynamic range of 7 orders of magnitude.     

Stereocontrol in radical processes through the exocyclic effect: dual role of triethylboron as radical initiator and in situ derivatization agent

[structure in text] The diastereoselectivity of radical processes involving 1,3-diols is increased significantly with a simple and efficient strategy using the exocyclic effect. Boronate derivatives are successfully formed in situ by treatment of an equimolar amount of Et(3)B in the presence of oxygen. This step is followed by the mediation of a carbon-centered radical alpha to the cyclic boronate to give the anti reduced product with high stereocontrol. The sequence is also extended to beta-amino alcohols.     

Evaluation of diimine ligand exchange on Cu(I)

Four ligands have been prepared, 8,8-dimethyl-6,7,9-trihydropyrido[1,2-b]acridine and three 4,4',6,6'-tetrasubstituted derivatives of 2,2'-bipyrimidine where the substituents are methyl, phenyl, and p-tolyl. The corresponding [CuL(2)](+) salts of these ligands evidence nonequivalent NMR signals that allow an estimation of the ligand exchange barrier in both acetonitrile and chloroform solution. Lower barriers are found in the former solvent and attributed to solvent participation in the exchange process. Corresponding differences in the oxidation potentials of the complexes are explained in a similar manner. The electronic absorption properties of the complexes are also consistent with the steric and electronic properties of the ligands. [Cu(2c)(2)](PF(6)), where 2c = 4,4',6,6'-tetraphenyl-2,2'-bipyrimidine, was analyzed by X-ray diffraction and found to crystallize in the space group Pccn with a = 14.761(2) A, b = 15.007(2) A, c = 24.407(4) A, and Z = 4. The internal and external phenyl rings are disposed quite differently, with the internal rings interacting strongly with the orthogonal ligand.     

Advances in sample preparation in electromigration, chromatographic and mass spectrometric separation methods

The quality of sample preparation is a key factor in determining the success of analysis. While analysis of pharmaceutically important compounds in biological matrixes has driven forward the development of sample clean-up procedures in last 20 years, today's chemists face an additional challenge: sample preparation and analysis of complex biochemical samples for characterization of genotypic or phenotypic information contained in DNA and proteins. This review focuses on various sample pretreatment methods designed to meet the requirements for the analysis of biopolymers and small drugs in complex matrices. We discuss the advances in development of solid-phase extraction (SPE) sorbents, on-line SPE, membrane-based sample preparation, and sample clean-up of biopolymers prior to their analysis by mass spectrometry.     

High‐pressure polarized Raman spectra of Gd2(MoO4)3: phase transitions and amorphization

Polarized Raman spectra of a single crystal of gadolinium molybdate [Gd₂(MoO₄)₃] were obtained between 1 atm and 7 GPa. Using a mixture of alcohols as the pressure‐transmitting medium, YY, ZZ, XY components of scattering matrices were measured. The ZZ spectra were also obtained in argon. Five phase transitions and amorphization were identified. The first and second transitions are reversible, while amorphization is not. In alcohol, amorphization is observed above 6.5 GPa. With argon as the pressure‐transmitting medium, amorphization is progressive and begins above 3 GPa. The spectral changes with pressure affect the high wavenumber bands attributed to symmetric and antisymmetric MoO₄ stretching modes as well as the very low wavenumber modes such as librations of the tetrahedra. This means that both short‐range and long‐range organizations of the tetrahedra are involved in these phase transitions. The amorphization mechanism and its dependence on the pressure‐transmitting medium are discussed, and the steric hindrance between polyhedra is believed to be the most relevant mechanism. The TO and LO low wavenumber modes of A₁ symmetry, observed in the Y(ZZ)Y and Z(YY)Z geometries, respectively, below 50 cm⁻¹, soften continuously through the first three phases when increasing pressure. The strong A₂ mode observed in the Z(XY)Z spectra exhibits the same anomalous behavior by decreasing from 53 to 46 cm⁻¹ at 2 GPa. The softening of these modes is related to the orientation change of tetrahedra observed by ab initio calculations when the volume of the cell is decreased. These orientation changes can explain the wavenumber decrease of the Mo O stretching modes above 2 GPa, which indicates an increase of Mo coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Study of the dynamic and static behavior of de vortex plasma torches: Part II: Well-tye cathode

This work was devoted to the study of the dynamic and static behavior of de vortex plasma torch with a well-type cathode (power level below 100 kW). The dynamic behavior of the torch was characterized by the fulctuations of arc voltage and current, plasma jet radiation, and acoustic pressure. Characteristic frequencies of the arc root movement inside the torch were observed. By numerical simulation (with the numerical codeMelodie, it was shown that the position of the erosion diameter) of the axial velocity along the cathode channel near the wall. The static behavior of the torch was inverstigated for different cathode designs. The variations of voltage U with arc current I, gas flow rate G nature of the gas and cathode design were represented by semiempirical relationships established between dimensionless numbers. By dimensional analysis, the behavior of this torch was compared with that of two powerful torches: the Aerospatiale and the Plasma Energy Corporation torches.     

Relaxation of the Ne(2p1) level and populations of Ne(1s2) and Ne(1s4) in an afterglow

Radiation trapping of the transition 2p₁-1s₂ of neon has been demonstrated during laser-induced fluorescence in a pulsed microwave discharge through neon. The population of Ne(1s₂) atoms is deduced. Selective excitation is useful for the determination of lifetimes and cross sections of collisions with neutral atoms. The results may be utilized in processes for the creation of metastable atoms.